US 2006O183866A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2006/0183866A1 Pohl et al. (43) Pub. Date: Aug. 17, 2006

(54) BLOCKED MERCAPTOSILANE COUPLING (60) Provisional application No. 60/056,566, filed on Aug. AGENTS FOR FILLED RUBBERS 21, 1997. (76) Inventors: Eric R. Pohl, Mount Kisco, NY (US); Publication Classification Richard W. Cruse, Yorktown Heights, NY (US); Keith J. Weller, North (51) Int. Cl. Greenbush, NY (US); Robert J. CSF I32/00 (2006.01) Pickwell, Tonawanda, NY (US) (52) U.S. Cl...... 525/326.1; 524/146; 524/167; 524/168; 524/173; 524/262: Correspondence Address: 524/265; 524/267: 524/302: DILWORTH & BARRESE, LLP 524/306; 524/307; 524/308; 333 EARLE OVINGTON BLVD. 524/309; 524/311:524/392: UNIONDALE, NY 11553 (US) 524/393; 524/401

(21) Appl. No.: 11/398,125 (57) ABSTRACT (22) Filed: Apr. 5, 2006 Blocked mercaptosilanes are provided in which the blocking Related U.S. Application Data group contains an unsaturated heteroatom or carbon chemi cally bound directly to sulfur via a single bond. This (60) Continuation of application No. 09/986,512, filed on blocking group optionally may be substituted with one or Nov. 9, 2001, which is a division of application No. more carboxylate or functional groups. 09/284.841, filed on Apr. 21, 1999, now Pat. No. These silanes are used in manufacture of inorganic filled 6,414,061, filed as 371 of international application rubbers, with the silanes deblocked by a deblocking agent. No. PCT/US98/17391, filed on Aug. 21, 1998. Synthesis of the blocked mercaptosilanes is also provided. US 2006/0183866 A1 Aug. 17, 2006

BLOCKED MERCAPTOSILANE COUPLNG mercaptosilane coupling agents, nor does it disclose or AGENTS FOR FILLED RUBBERS Suggest the use of these compounds in any way which would give rise to the advantages of using them as a Source of latent CROSS REFERENCE TO RELATED mercaptosilane. APPLICATION 0006 U.S. Pat. Nos. 4,519,430 to Ahmad et al. and U.S. 0001. This is a continuation of co-pending application no. Pat. No. 4,184,998 to Shippy et al. disclose the blocking of 09/986,512 filed on Nov. 9 2001, which is a division of a mercaptosilane with an to form a solid which is application Ser. No. 09/284.841, filed Apr. 21, 1999, now added to a tire composition, which mercaptain reacts into the U.S. Pat. No. 6,414,061 issued on Jul. 2, 2002, which is a tire during heating, which could happen at any time during 371 of PCT/US98/17391, Aug. 21, 1998, which claims processing since this is a thermal mechanism. The purpose priority to U.S. Provisional Patent Application No. 60/056, of this silane is to avoid the sulfur smell of the mercaptosi 566, filed Aug. 21, 1997. lane, not to improve the processing of the tire. Moreover, the isocyanate used has toxicity issues when used to make the FIELD OF THE INVENTION silane and when released during rubber processing. 0002 This invention relates to sulfur silane coupling 0007 U.S. Pat. No. 3,957,718 to Porchet et al. discloses agents which are latent, that is, they are in a state of reduced compositions containing silica, phenoplasts or aminoplasts, activity until Such a time as one finds it useful to activate and silanes, such as Xanthates, thioxanthates, and dithiocar them. The invention also relates to the manufacture of bamates; however, the prior art does not disclose or Suggest rubbers including inorganic fillers and these silane coupling the use of these silanes as latent mercaptosilane coupling agents, as well as to the manufacture of the silanes. agents, nor does it suggest or disclose the advantage of using them as a source of latent mercaptosilane. There remains a BACKGROUND need for effective latent coupling agents which exhibit the 0003. The majority of art in the use of sulfur-containing advantages of mercaptosilanes without exhibiting the dis coupling agents in rubber involves silanes containing one or advantages Such as described herein. more of the following chemical bond types: S-H (mer capto), S S ( or polysulfide), or C=S (thiocarbo SUMMARY OF THE INVENTION nyl). Mercaptosilanes have offered Superior coupling at 0008. The silanes of the present invention are mercap substantially reduced loadings; however, their high chemical tosilane derivatives in which the mercapto group is blocked reactivity with organic polymers leads to unacceptably high ("blocked mercaptosilanes'), i.e., the mercapto hydrogen Viscosities during processing and premature curing (Scorch). atom is replaced by another group (hereafter referred to as Their undesirability is aggravated by their odor. As a result, “blocking group'). Specifically, the silanes of the present other, less reactive coupling agents have been found. Hence, invention are blocked mercaptosilanes in which the blocking a compromise must be found between coupling and the group contains an unsaturated heteroatom or carbon chemi associated final properties, processability, and required load cally bound directly to sulfur via a single bond. This ing levels, which invariably leads to the need to use sub blocking group optionally may be substituted with one or stantially higher coupling agent loadings than would be more carboxylate ester or carboxylic acid functional groups. required with mercaptosilanes, and often also to the need to The use of these silanes in the manufacture of inorganic deal with less than optimal processing conditions, both of filled rubbers is taught wherein they are deblocked by the which lead to higher costs. use of a deblocking agent during the manufacturing process. 0004 The prior art discloses acylthioalkyl silanes, such The manufacture of Such silanes is taught as well. as CHC(=O)S(CH), Si(OR) (M. G. Voronkov et al. in Inst. Org. Khim., Irkutsk, Russia) and DETAILED DESCRIPTION OF THE HOC(=O)CHCHC(=O)S(CH.).Si(OC.H.). (U.S. Pat. INVENTION No.3,922,436 to R. Bell et al.). Takeshita and Sugawara disclosed in Japanese Patent JP 63270751 A2 the use of Silane Structures compounds represented by the general formula 0009. The blocked mercaptosilanes can be represented by CH=C(CH,)C(=O)S(CH4), Si(OCH,), in tire tread the Formulae (1-2): compositions; but these compounds are not desirable because the unsaturation C.f3 to the of the (ROC(=O))-(G). Y-S-G-(SIXs), (1); and has the undesirable potential to polymerize during I(X,Si), Gl-IY-IS-G-SiXs.l. (2) the compounding process or during storage. wherein 0005 Prior art by Yves Bomal and Olivier Durel in 0010 Y is a polyvalent species (Q) A(=E), preferably Australian Patent AU-A-10082/97 discloses the use in rub selected from the group consisting of —C(=NR)—: ber of silanes of the structure represented by RX-Si (Alk), (Ar), S(C=O) R where R" is phenyl or : X is halogen, alkoxy, cycloalkoxy, acyloxy, or OH: Alk is alkyl, Ar is aryl; R is alky, alkenyl, or aryl; n is 0 to 2; and m and p are each 0 or 1, but not both Zero. This prior art, however, stipulates that compositions of the structures of Formula (1P) must be used in conjunction with functional ized siloxanes. In addition, the prior art does not disclose or Suggest the use of compounds of Formula (1P) as latent US 2006/0183866 A1 Aug. 17, 2006

a “dithiocarbamate ester silane'); thiosulfonate ester, (any silane with this is a silane'); thiosulfate ester, —O—S(=O)2S - (any silane with this functional group is the atom (A) attached to the unsaturated heteroatom (E) is a “thiosulfate ester silane'); thiosulfamate ester, ( N ) attached to the sulfur, which in turn is linked via a group G S(=O)S - (any silane with this functional group is a to the silicon atom; “thiosulfamate ester silane'); thiosulfinate ester, 0011 each R is chosen independently from hydrogen, —S(=O)S - (any silane with this functional group is a straight, cyclic, or branched alkyl that may or may not “thiosulfinate ester silane'); thiosulfate ester, —O—S contain unsaturation, alkenyl groups, aryl groups, and (=O)S (any silane with this functional group is a “thio aralkyl groups, with each R containing from 1 to 18 carbon sulfite ester silane'); thiosulfimate ester, ( N )S(=O)— atoms; S— (any silane with this functional group is a “thiosulfimate 0012 each G is independently a monovalent or polyva ester silane'); thiophosphate ester, P(=O)(O ), (S-) (any lent group derived by Substitution of alkyl, alkenyl, aryl, or silane with this functional group is a “thiophosphate ester aralkyl wherein G can contain from 1 to 18 carbon atoms, silane'); dithiophosphate ester, P(=O)(O )(S-), or with the proviso that G is not such that the silane would P(=S)(O—),(S ) (any silane with this functional group is contain an O.B-unsaturated carbonyl including a carbon a “dithiophosphate ester silane'); trithiophosphate ester, carbon double bond next to the thiocarbonyl group, and if G P(=O)(S ), or P(=S)(O )(S ), (any silane with this directly bonded to Y is univalent (i.e., if p=0), G can be a functional group is a “trithiophosphate ester silane'); hydrogen atom; tetrathiophosphate ester P(=S)(S-) (any silane with this functional group is a “tetrathiophosphate ester silane'); 0013 X is independently selected from the group con thiophosphamate ester, —P(=O)( N )(S-) (any silane sisting of Cl, Br, RO , RC(=O)C) , RC=NO , with this functional group is a “thiophosphamate ester RNO or RN —R, —(OSiR),(OSiR) wherein each silane'); dithiophosphamate ester, —P(=S)( N—)(S ) R and G is as above and at least one X is not —R; (any silane with this functional group is a “dithiophospha 0014 Q is oxygen, sulfur, or ( NR—); mate ester silane); thiophosphoramidate ester, (—N—) P(=O)(O )(S ) (any silane with this functional group is 0.015 A is carbon, sulfur, phosphorus, or sulfonyl: a “thiophosphoramidate ester silane); dithiophosphorami 0016 E is oxygen, sulfur, or NR; date ester, ( N )P(=O)(S ), or ( N )P(=S)(O-) (S—) (any silane with this functional group is a "dithio 0017 p is 0 to 5; r is 1 to 3; Z is 0 to 2: q is 0 to 6; a is phosphoramidate ester silane'); trithiophosphoramidate 0 to 7: b is 1 to 3: j is 0 to 1, but it may be 0 only if p is 1: ester, ( N )P(=S)(S-) (any silane with this functional c is 1 to 6, preferably 1 to 4; t is 0 to 5; s is 1 to 3; k is 1 group is a “trithiophosphoramidate ester silane'). to 2; with the provisos that (A) if A is carbon, sulfur, or sulfonyl, then (i) a+b=2 and (ii) k=1; (B) if A is phosphorus, 0020 Novel silanes of the present invention are those then a +b=3 unless both (i) ca 1 and (ii) b=1, in which case a=c+1; and (C) if A is phosphorus, then k is 2. 0018. As used herein, “alkyl includes straight, branched, and cyclic alkyl groups, and 'alkenyl includes Straight, branched, and cyclic alkenyl groups containing one or more carbon-carbon double bonds. Specific include methyl, ethyl, propyl, isobutyl, and specific aralkyls include phenyl, tolyl, and phenethyl. As used herein, “cyclic alkyl or “cyclic alkenyl also includes bicyclic and higher cyclic structures, as well as cyclic structures further substituted with alkyl groups. Representative examples include nor bornyl, norbornenyl, ethylnorbornyl, ethylnorbornenyl, eth ylcyclohexyl, ethylcyclohexenyl, and cyclohexylcyclo hexyl. 0.019 Representative examples of the functional groups 0021 Another novel silane would be one wherein Y is ( YS ) present in the silanes of the present invention —C(=O)— wherein G has a primary carbon attached to the include thiocarboxylate ester, —C(=O)S (any silane with carbonyl and is a C-C alkyl, more preferably a C-Cs this functional group is a “thiocarboxylate ester silane'); alkyl. dithiocarboxylate. —C(=S)S (any silane with this func 0022. Another preferred novel structure is of the form tional group is a “dithiocarboxylate ester silane'); thiocar bonate ester, —O C(=O)S (any silane with this func hydrocarbon.XSiGSC(=O)CC(=O)SGSIX, wherein G is a divalent tional group is a “thiocarbonate ester silane'); dithiocarbonate ester, —S C(=O)S- and 0023 Examples of G include —(CH), wherein n is 1 —O—C(=S)S— (any silane with this functional groups is to 12, diethylene cyclohexane, 1,2,4-triethylene cyclohex a “dithiocabonate ester silane'); trithiocarbonate ester, ane, and diethylene benzene. It is preferred that the sum of —S-C(=S)S— (any silane with this functional group is a the carbon atoms within the G groups within the molecule “trithiocarbonate ester silane); dithiocarbamate ester, are from 3 to 18, more preferably 6 to 14. This amount of ( N )C(=S)S (any silane with this functional group is carbon in the blocked mercaptosilane facilitates the disper US 2006/0183866 A1 Aug. 17, 2006 sion of the inorganic filler into the organic polymers, thereby propyldiethylthiophosphinate; tris-(3-triethoxysilyl-1- improving the balance of properties in the cured filled propyl)tetrathiophosphate: bis-(3-triethoxysilyl-1- rubber. propyl)methyltrithiophosphonate; bis-(3-triethoxysilyl-1- propyl)ethyltrithiophosphonate; 3-triethoxysilyl-1- 0024 Preferable R groups are alkyls of C to C and H. propyldimethyldithiophosphinate; 3-triethoxysilyl-1- 0.025 Specific examples of X are methoxy, ethoxy, isobu propyldiethyldithiophosphinate; tris-(3- toxy, propoxy, isopropoxy, acetoxy, and oximato. Methoxy, methyldimethoxysilyl-1-propyl)trithiophosphate; bis-(3- acetoxy, and ethoxy are preferred. At least one X must be methyldimethoxysilyl-1-propyl)methyldithiophosphonate; reactive (i.e., hydrolyzable). bis-(3-methyldimethoxysilyl-1-propyl)ethyldithiophospho nate; 3-methyldimethoxysilyl-1-propyldimethylthiophos 0026. Preferred embodiments are wherein p is 0 to 2: X phinate: 3-methyldimethoxysilyl-1-propyldiethylthiophos is RO or RC(=O)C)—; R is hydrogen, phenyl, isopropyl. phinate; 3-triethoxysilyl-1-propylmethylthiosulphate: cyclohexyl, or isobutyl: G is a substituted phenyl or substi 3-triethoxysilyl-1-propylmethanethiosulphonate; 3-triethox tuted Straight chain alkyl of C to C. The most preferred ysilyl-1-propylethanethiosulphonate; 3-triethoxysilyl-1-pro embodiments include those wherein p is zero, X is ethoxy, pylbenzenethiosulphonate; 3-triethoxysilyl-1-propyltolu and G is a C-C alkyl derivative. enethiosulphonate; 3-triethoxysilyl-1- propylnaphthalenethiosulphonate; 3-triethoxysilyl-1- 0027 Representative examples of the silanes of the propylxylenethiosulphonate; present invention include: 2-triethoxysilyl-1-ethyl thioac triethoxysilylmethylmethylthiosulphate; triethoxysilylmeth etate: 2-trimethoxysilyl-1-ethyl thioacetate: 2-(meth ylmethenethiosulphonate; triethoxysilylmethylethaneth yldimethoxysilyl)-1-ethyl thioacetate: 3-trimethoxysilyl-1- iosulphonate; triethoxysilylmethylbenzenethiosulphonate: propyl thioacetate; triethoxysilylmethyl thioacetate; triethoxysilylmethyltolunethiosulphonate; triethoxysilylm trimethoxysilylmethyl thioacetate; triisopropoxysilylmethyl ethylnaphthalenethiosulphonate; and triethoxysilylmeth thioacetate; methyldiethoxysilylmethyl thioacetate; meth ylxylenethiosulphonate. yldimethoxysilylmethyl thioacetate; methyldiisopropoxysi lylmethyl thioacetate; dimethylethoxysilylmethyl thioac 0028 Mixtures of various blocked mercaptosilanes may etate; dimethylmethoxysilylmethyl thioacetate; be used, including wherein synthetic methods result in a dimethylisopropoxysilylmethyl thioacetate; 2-triisopro distribution of various silanes or where mixes of blocked poxysilyl-1-ethyl thioacetate: 2-(methyldiethoxysilyl)-1- mercaptosilanes are used for their various blocking or leav ethyl thioacetate: 2-(methyldiisopropoxysilyl)-1-ethyl thio ing functionalities. Moreover, it is understood that the partial acetate; 2-(dimethylethoxysilyl)-1-ethyl thioacetate; hydrolyzates of these blocked mercaptosilanes (i.e., blocked 2-(dimethylmethoxysilyl)-1-ethyl thioacetate: 2-(dimethyl mercaptosiloxanes) may also be encompassed by the isopropoxysilyl)-1-ethyl thioacetate; 3-triethoxysilyl-1-pro blocked mercaptosilanes herein, in that these partial hydro pyl thioacetate, 3-triisopropoxysilyl-1-propyl thioacetate; lyzates will be a side product of most methods of manufac 3-methyldiethoxysilyl-1-propyl thioacetate; 3-meth ture of the blocked mercaptosilane or can occur upon storage yldimethoxysilyl-1-propyl thioacetate; 3-methyldiisopro of the blocked mercaptosilane, especially in humid condi poxysilyl-1-propylthioacetate: 1-(2-triethoxysilyl-1-ethyl)- tions. 4-thioacetylcyclohexane: 1-(2-triethoxysilyl-1-ethyl)-3- thioacetylcyclohexane: 2-triethoxysilyl-5- 0029. The silane, if liquid, may be loaded on a carrier, thioacetylnorbornene; 2-triethoxysilyl-4- Such as a porous polymer, carbon black, or silica so that it thioacetylnorbornene; 2-(2-triethoxysilyl-1-ethyl)-5- is in solid form for delivery to the rubber. In a preferred thioacetylnorbornene; 2-(2-triethoxysilyl-1-ethyl)-4- mode, the carrier would be part of the inorganic filler to be thioacetylnorbornene; 1-(1-oxo-2-thia-5- used in the rubber. triethoxysilylpenyl)benzoic acid: 6-triethoxysilyl-1-hexyl Manufacture of Silanes thioacetate: 1-triethoxysilyl-5-hexylthioacetate; 8-triethox ysilyl-1-octyl thioacetate: 1-triethoxysilyl-7-octyl thioac 0030 The methods of preparation for blocked mercap etate: 6-triethoxysilyl-1-hexyl thioacetate: 1-triethoxysilyl tosilanes can involve esterification of sulfur in a sulfur 5-octyl thioacetate; 8-trimethoxysilyl-1-octyl thioacetate; containing silane and direct incorporation of the thioester 1-trimethoxysilyl-7-octyl thioacetate; 10-triethoxysilyl-1- group into a silane, either by Substitution of an appropriate decyl thioacetate: 1-triethoxysilyl-9-decyl thioacetate: 1-tri leaving group or by addition across a carbon-carbon double ethoxysilyl-2-butyl thioacetate: 1-triethoxysilyl-3-butyl bond. Illustrative examples of synthetic procedures for the thioacetate: 1-triethoxysilyl-3-methyl-2-butyl thioacetate; preparation of thioester silanes would include: Reaction 1) 1-triethoxysilyl-3-methyl-3-butyl thioacetate; 3-trimethox the reaction between a mercaptosilane and an acid anhydride ysilyl-1-propyl thiooctanoate: 3-triethoxysilyl-1-propyl corresponding to the thioester group present in the desired thiopalmitate; 3-triethoxysilyl-1-propylthiooctanoate: 3-tri product; Reaction 2) reaction of an alkali metal salt of a ethoxysilyl-1-propylthiobenzoate, 3-triethoxysilyl-1-propyl mercaptosilane with the appropriate acid anhydride or acid thio-2-ethylhexanoate: 3-methyldiacetoxysilyl-1-propyl halide; Reaction 3) the transesterification between a mer thioacetate; 3-triaetoxysilyl-1-propylthioacetate: 2-methyl captosilane and an ester, optionally using any appropriate diacetoxysilyl-1-ethyl thioacetate; 2-triacetoxysilyl-1-ethyl catalyst Such as an acid, base, tin compound, titanium thioacetate: 1-methyldiacetoxysilyl-1-ethyl thioacetate; compound, transition metal salt, or a salt of the acid corre 1-triacetoxysilyl-1-ethylthioacetate; tris-(3-triethoxysilyl-1- sponding to the ester, Reaction 4) the transesterification propyl)trithiophosphate; bis-(3-triethoxysilyl-1-propyl)m- between a thioester silane and another ester, optionally using ethyldithiophosphonate; bis-(3-triethoxysilyl-1-propyl)eth any appropriate catalyst Such as an acid, base, tin compound, yldithiophosphonate; 3-triethoxysilyl-1- titanium compound, transition metal salt, or a salt of the acid propyldimethylthiophosphinate; 3-triethoxysilyl-1- corresponding to the ester; Reaction 5) the transesterification US 2006/0183866 A1 Aug. 17, 2006 between a 1-sila-2-thiacyclopentane or a 1-sila-2-thiacyclo be used with the process to limit temperature. Alternatively, hexane and an ester, optionally using any appropriate cata the process could be run at reduced pressure. It would be lyst Such as an acid, base, tin compound, titanium com useful to use up to a twofold excess or more of the acid pound, transition metal salt, or a salt of the acid anhydride which would be distilled out of the mixture after corresponding to the ester; Reaction 6) the free radical all of the more volatile reaction coproducts, consisting of addition of a thioacid across a carbon-carbon double bond of acids and nonsilane , have been distilled out. This an -functional silane, catalyzed by UV light, heat, or excess of acid anhydride would serve to drive the reaction to the appropriate free radical initiator wherein, if the thioacid completion, as well as to help drive the coproducts out of the is a thiocarboxylic acid, the two reagents are brought into reaction mixture. At the completion of the reaction, distil contact with each other in Such a way as to ensure that whichever reagent is added to the other is reacted substan lation should be continued to drive out the remaining acid tially before the addition proceeds; and Reaction 7) the anhydride. The product optionally could be distilled. reaction between an alkali metal salt of a thioacid with a 0034 Reactions 2 and 9 can be carried out in two steps. haloalkylsilane. The first step would involve conversion of the mercaptosi 0031 Acid halides include but are not limited to, in lane to a corresponding metal derivative. Alkali metal addition to organic acid halides, inorganic acid halides. Such derivatives, especially sodium or also potassium and as POT, SOT, SOT COT, CST, PST and PT. lithium, are preferable. The metal derivative would be wherein T is a halide. Acid anhydrides include but are not prepared by adding the alkali metal or a strong base derived limited to, in addition to organic acid anhydrides (and their from the alkali metal to the mercaptosilane. The reaction Sulfur analogs), inorganic acid anhydrides such as SO SO. would occur at ambient temperature. Appropriate bases POs, PSs, HSO, CO, COS, and CS. would include alkali metal alkoxides, , hydrides, and 0032 Illustrative examples of synthetic procedures for mercaptides. Alkali metal organometallic reagents would the preparation of thiocarboxylate-functional silanes would also be effective. Grignard reagents would yield magnesium include: Reaction 8) the reaction between a mercaptosilane derivatives, which would be another alternative. Solvents, and a carboxylic acid anhydride corresponding to the thio Such as toluene, Xylene, benzene, aliphatic hydrocarbons, carboxylate group present in the desired product; Reaction , and alcohols could be used to prepare the alkali metal 9) reaction of an alkali metal salt of a mercaptosilane with derivatives. Once the alkali metal derivative is prepared, any the appropriate carboxylic acid anhydride or acid halide; alcohol present would need to be removed. This could be Reaction 10) the transesterification between a mercaptosi done by distillation or evaporation. Alcohols, such as metha lane and a carboxylate ester, optionally using any appropri nol, ethanol, propanol, isopropanol, butanol, isobutanol, and ate catalyst, such as an acid, base, tin compound, titanium t-butanol may be removed by azeotropic distillation with compound, transition metal salt, or a salt of the acid corre benzene, toluene, Xylene, or aliphatic hydrocarbons. Toluene sponding to the carboxylate ester; Reaction 11) the transes and xylene are preferable; toluene is most preferable. The terification between a thiocarboxylate-functional silane and second step in the overall process would be to add to this another ester, optionally using any appropriate catalyst, Such Solution, with stirring, the acid chloride or acid anhydride at as an acid, base, tin compound, titanium compound, transi temperatures between -20° C. and the boiling point of the tion metal salt, or a salt of the acid corresponding to the other mixture, preferably at temperatures between 0° C. and ester, Reaction 12) the transesterification between a 1-sila ambient temperature. The product would be isolated by 2-thiacyclopentane or a 1-sila-2-thiacyclohexane and a car removing the salt and solvent. It could be purified by boxylate ester, optionally using any appropriate catalyst, distillation. Such as an acid, base, tin compound, titanium compound, transition metal salt, or a salt of the acid corresponding to the 0035) Reactions 3 and 10 could be carried out by distill carboxylate ester; Reaction 13) the free radical addition of a ing a mixture of the mercaptosilane and the ester and thiocarboxylic acid across a carbon-carbon double bond of optionally a solvent and/or a catalyst. Appropriate boiling an alkene-functional silane, catalyzed by UV light, heat, or temperatures of the mixture would be above 100° C. This the appropriate free radical initiator; and Reaction 14) the process leads to a chemical reaction in which the mercapto reaction between an alkali metal salt of a thiocarboxylic acid group of the mercaptosilane is esterified to the thioester with a haloalkylsilane. silane analog with release of an equivalent of the corre sponding alcohol. The reaction is driven by the removal of 0033 Reactions 1 and 8 can be carried out by distilling a the alcohol by distillation, either as the more volatile spe mixture of the mercaptosilane and the acid anhydride and cies, or as an azeotrope with the ester. For the more volatile optionally a solvent. Appropriate boiling temperatures of the esters the distillation is suitably carried out at ambient mixture are in the range of 60° to 200° C.; preferably 70° to pressure to reach temperatures Sufficient to drive the reaction 170° C.: optionally 50° to 250° C. This process leads to a toward completion. For less Volatile esters, Solvents, such as chemical reaction in which the mercapto group of the toluene, Xylene, glyme, and diglyme could be used with the mercaptosilane is esterified to the thioester silane analog process to limit temperature. Alternatively, the process could with release of an equivalent of the corresponding acid. The be run at reduced pressure. It is useful to use up to a twofold acid typically is more volatile than the acid anhydride. The excess or more of the ester, which would be distilled out of reaction is driven by the removal of the more volatile acid the mixture after all of the alcohol coproduct has been by distillation. For the more volatile acid anhydrides, such as distilled out. This excess ester would serve to drive the acetic anhydride, the distillation preferably is carried out at reaction to completion as well as to help drive the coproduct ambient pressure to reach temperatures sufficient to drive the alcohol out of the reaction mixture. At the completion of the reaction toward completion. For less volatile materials, reaction, distillation would be continued to drive out the Solvents such as toluene, Xylene, glyme, and diglyme could remaining ester. The product optionally could be distilled.

US 2006/0183866 A1 Aug. 17, 2006 repeated. The preferred number of thiolacetic additions for the thioacid salt used. If the haloalkylsilane is a bromoalkyl total reaction quantities of about one to about four kilograms silane or a chloroalkylsilane in which the chlorine atom is is two, with about one-third of the total thiolacetic acid used allylic or benzylic, temperature reductions of 30° to 60° C. in the first addition and the remainder in the second. For total are appropriate relative to those appropriate for nonbenzylic quantities in the range of about four to ten kilograms, a total or nonallylic chloroalkylsilanes because of the greater reac of three thiolacetic additions is preferred, the distribution tivity of the bromo group. Bromoalkylsilanes are preferred being approximately 20 percent of the total used in the first over chloroalkylsilanes because of their greater reactivity, addition, approximately 30 percent in the second addition, lower temperatures required, and greater ease in filtration or and the remainder in the third addition. For larger scales centrifugation of the coproduct alkali metal halide. This involving thiolacetic acid and alkene-functional silanes, it is preference, however, can be overridden by the lower cost of preferable to use more than a total of three thiolacetic the chloroalkylsilanes, especially for those containing the additions and, more preferably, to add the reagents in the halogen in the allylic or benzylic position. For reactions reverse order. Initially, the total quantity of thiolacetic acid between straight chain chloroalkylethoxysilanes and sodium is brought to reflux. This is followed by continuous addition thiocarboxylates to form thiocarboxylate ester ethoxysi of the alkene-functional silane to the thiolacetic acid at such lanes, it is preferable to use ethanol at reflux for 10 to 20 a rate as to bring about a Smooth but vigorous reaction rate. hours if 5 to 20 percent mercaptosilane is acceptable in the The catalyst, preferably di-t-butylperoxide, can be added in product. Otherwise, diglyme would be an excellent choice, Small portions during the course of the reaction or as a in which the reaction would be run preferably in the range continuous flow. It is best to accelerate the rate of catalyst of 80° to 120° C. for one to three hours. Upon completion addition as the reaction proceeds to completion to obtain the of the reaction the salts and solvent should be removed, and highest yields of product for the lowest amount of catalyst the product may be distilled to achieve higher purity. required. The total quantity of catalyst used should be 0.5 to 2 percent of the total mass of reagents used. Whichever 0040. If the salt of the thioacid to be used in Reactions 7 method is used, the reaction is followed up by a vacuum and 14 is not commercially available, its preparation may be stripping process to remove volatiles and unreacted thiolace accomplished by one of two methods, described below as tic acid and silane. The product may be purified by distil Method A and Method B. Method A involves adding the lation. alkali metal or a base derived from the alkali metal to the thioacid. The reaction occurs at ambient temperature. 0.039 Methods to run Reactions 7 and 14 can be carried Appropriate bases include alkali metal alkoxides, hydrides, out in two steps. The first step involves preparation of a salt carbonates, and bicarbonates. Solvents, such as toluene, of the thioacid. Alkali metal derivatives are preferred, with Xylene, benzene, aliphatic hydrocarbons, ethers, and alco the sodium derivative being most preferred. These salts hols may be used to prepare the alkali metal derivatives. In would be prepared as solutions in solvents in which the salt Method B, acid chlorides or acid anhydrides would be is appreciably soluble, but Suspensions of the salts as Solids converted directly to the salt of the thioacid by reaction with in solvents in which the salts are only slightly soluble are the alkali metal or hydrosulfide. Hydrated or partially also a viable option. Alcohols, such as propanol, isopro hydrous alkali metal sulfides or hydrosulfides are available: panol, butanol, isobutanol, and t-butanol, and preferably however, anhydrous or nearly anhydrous alkali metal Sul methanol and ethanol are useful because the alkali metal fides or hydrosulfides are preferred. Hydrous materials can salts are slightly soluble in them. In cases where the desired be used, however, but with loss in yield and hydrogen sulfide product is an alkoxysilane, it is preferable to use an alcohol formation as a coproduct. The reaction involves addition of corresponding to the silane to prevent trans the acid chloride or acid anhydride to the solution or esterification at the silicon ester. Alternatively, nonprotic suspension of the alkali metal sulfide and/or hydrosulfide Solvents can be used. Examples of appropriate solvents are and heating at temperatures ranging from ambient to the ethers or polyethers such as glyme, diglyme, and dioxanes; reflux temperature of the solvent for a period of time N,N-dimethylformamide: N,N-dimethylacetamide; dimeth Sufficient largely to complete the reaction, as evidenced by ylsulfoxide: N-methylpyrrolidinone; or hexamethylphos the formation of the coproduct salts. phoramide. Once a solution, Suspension, or combination thereof of the salt of the thioacid has been prepared, the 0041) If the alkali metal salt of the thioacid is prepared in second step is to react it with the appropriate haloalkylsilane. Such a way that an alcohol is present, either because it was This may be accomplished by stirring a mixture of the used as a solvent, or because it formed, as for example, by haloalkylsilane with the Solution, Suspension, or combina the reaction of a thioacid with an alkali metal alkoxide, it tion thereof of the salt of the thioacid at temperatures may be desirable to remove the alcohol if a product low in corresponding to the liquid range of the Solvent for a period mercaptosilane is desired. In this case, it would be necessary of time sufficient to complete substantially the reaction. to remove the alcohol prior to reaction of the salt of the Preferable temperatures are those at which the salt is appre thioacid with the haloalkylsilane. This could be done by ciably soluble in the solvent and at which the reaction distillation or evaporation. Alcohols, such as methanol, proceeds at an acceptable rate without excessive side reac ethanol, propanol, isopropanol, butanol, isobutanol, and tions. With reactions starting from chloroalkylsilanes in t-butanol are preferably removed by azeotropic distillation which the chlorine atom is not allylic or benzylic, preferable with benzene, toluene, Xylene, or aliphatic hydrocarbons. temperatures are in the range of 60° to 160° C. Reaction Toluene and xylene are preferred. times can range from one or several hours to several days. Utility For alcohol solvents where the alcohol contains four carbon atoms or fewer, the most preferred temperature is at or near 0042. The blocked mercaptosilanes described herein are reflux. When diglyme is used as a solvent, the most preferred useful as coupling agents for organic polymers (i.e., rubbers) temperature is in the range of 70° to 120° C., depending on and inorganic fillers. The blocked mercaptosilanes are US 2006/0183866 A1 Aug. 17, 2006 unique in that the high efficiency of the mercapto group can important is that regardless of the blocking group initially be utilized without the detrimental side effects typically present on the blocked mercaptosilane and regardless of the associated with the use of mercaptosilanes, such as high deblocking agent used, the initially Substantially inactive processing viscosity, less than desirable filler dispersion, (from the standpoint of coupling to the organic polymer) premature curing (scorch), and odor. These benefits are blocked mercaptosilane is substantially converted at the accomplished because the mercaptain group initially is non desired point in the rubber compounding procedure to the reactive because of the blocking group. The blocking group active mercaptosilane. It is noted that partial amounts of the Substantially prevents the silane from coupling to the nucleophile may be used (i.e., a stoichiometric deficiency), organic polymer during the compounding of the rubber. if one were to deblock only part of the blocked mercaptosi Generally, only the reaction of the silane —SiX group with lane to control the degree of Vulcanization of a specific the filler can occur at this stage of the compounding process. formulation. Thus, substantial coupling of the filler to the polymer is 0045 Water typically is present on the inorganic filler as precluded during mixing, thereby minimizing the undesir a hydrate, or bound to a filler in the form of a hydroxyl able premature curing (scorch) and the associated undesir group. The deblocking agent could be added in the curative able increase in viscosity. One can achieve better cured filled package or, alternatively, at any other stage in the com rubber properties, such as a balance of high modulus and pounding process as a single component. Examples of abrasion resistance, because of the avoidance of premature curing. nucleophiles would include any primary or secondary , or amines containing C=N double bonds, such as 0043. In use, one or more of the blocked mercaptosilanes or guanidines, with the proviso that said are mixed with the organic polymer before, during, or after contains at least one N-H (nitrogen-hydrogen) bond. the compounding of the filler into the organic polymer. It is Numerous specific examples of guanidines, amines, and preferred to add the silanes before or during the compound imines well known in the art, which are useful as compo ing of the filler into the organic polymer, because these nents in curatives for rubber, are cited in J. Van Alphen, silanes facilitate and improve the dispersion of the filler. The Rubber Chemicals (Plastics and Rubber Research Institute total amount of silane present in the resulting combination TNO, Delft, Holland, 1973). Some examples include N,N'- should be about 0.05 to about 25 parts by weight per hundred diphenylguanidine, N,N',N'-triphenylguanidine, N,N'-di parts by weight of organic polymer (phr), more preferably 1 ortho-tolylguanidine, orthobiguanide, hexamethylenetetra to 10 phr. Fillers can be used in quantities ranging from mine, cyclohexylethylamine, dibutylamine, and 4,4'- about 5 to 100 phr, more preferably from 25 to 80 phr. diaminodiphenylmethane. Any general acid catalysts used to 0044) When reaction of the mixture to couple the filler to transesterify esters, such as Bronsted or Lewis acids, could the polymer is desired, a deblocking agent is added to the be used as catalysts. mixture to deblock the blocked mercaptosilane. The deblocking agent may be added at quantities ranging from 0046) The rubber composition need not be, but preferably about 0.1 to about 5 phr, more preferably in the range of is, essentially free of functionalized siloxanes, especially from 0.5 to 3 phr. If alcohol or water is present (as is those of the type disclosed in Australian Patent AU-A- common) in the mixture, a catalyst (e.g., tertiary amines, 10082/97, which is incorporated herein by reference. Most Lewis acids, or ) may be used to initiate and promote preferably, the rubber composition is free of functionalized the loss of the blocking group by hydrolysis or alcoholysis siloxanes. to liberate the corresponding mercaptosilane. Alternatively, 0047. In practice, sulfur Vulcanized rubber products typi the deblocking agent may be a nucleophile containing a cally are prepared by thermomechanically mixing rubber hydrogen atom Sufficiently labile Such that the hydrogen and various ingredients in a sequentially stepwise manner atom could be transferred to the site of the original blocking followed by shaping and curing the compounded rubber to group to form the mercaptosilane. Thus, with a blocking form a Vulcanized product. First, for the aforesaid mixing of group acceptor molecule, an exchange of hydrogen from the the rubber and various ingredients, typically exclusive of nucleophile would occur with the blocking group of the sulfur and sulfur Vulcanization accelerators (collectively blocked mercaptosilane to form the mercaptosilane and the “curing agents'), the rubber(s) and various rubber com corresponding derivative of the nucleophile containing the pounding ingredients typically are blended in at least one, original blocking group. This transfer of the blocking group and often (in the case of silica filled low rolling resistance from the silane to the nucleophile could be driven, for tires) two, preparatory thermomechanical mixing stage(s) in example, by a greater thermodynamic stability of the prod Suitable mixers. Such preparatory mixing is referred to as ucts (mercaptosilane and nucleophile containing the block nonproductive mixing or nonproductive mixing steps or ing group) relative to the initial reactants (blocked mercap stages. Such preparatory nixing usually is conducted at tosilane and nucleophile). For example, if the nucleophile temperatures up to 140° to 200° C. and often up to 150° to were an amine containing an N-H bond, transfer of the 180° C. Subsequent to Such preparatory mix stages, in a final blocking group from the blocked mercaptosilane would mixing stage, sometimes referred to as a productive mix yield the mercaptosilane and one of several classes of stage, deblocking agent (in the case of this invention), curing amides corresponding to the type of blocking group used. agents, and possibly one or more additional ingredients are For example, carboxyl blocking groups deblocked by mixed with the rubber compound or composition, typically amines would yield amides, Sulfonyl blocking groups at a temperature in a range of 50° to 130° C., which is a deblocked by amines would yield sulfonamides, sulfinyl lower temperature than the temperatures utilized in the blocking groups deblocked by amines would yield Sulfona preparatory mix stages to prevent or retard premature curing mides, phosphonyl blocking groups deblocked by amines of the sulfur curable rubber, which is sometimes referred to would yield phosphonamides, phosphinyl blocking groups as scorching of the rubber composition. The rubber mixture, deblocked by amines would yield phosphinamides. What is Sometimes referred to as a rubber compound or composition, US 2006/0183866 A1 Aug. 17, 2006 typically is allowed to cool, Sometimes after or during a 0.055 (ii) 5 to 100 phr (parts per hundred rubber), process intermediate mill mixing, between the aforesaid preferably 25 to 80 phr, of particulate filler, wherein various mixing steps, for example, to a temperature of about preferably the filler contains 1 to 85 weight percent 50° C. or lower. When it is desired to mold and to cure the carbon black, rubber, the rubber is placed into the appropriate mold at about at least 130° C. and up to about 200° C., which will 0056 (iii) 0.05 to 20 parts by weight filler of at least cause the Vulcanization of the rubber by the mercapto groups one blocked mercaptosilane; on the mercaptosilane and any other free Sulfur sources in 0057 (B) subsequently blending therewith, in a final the rubber mixture. thermomechanical mixing step at a temperature to 50° to 130° C. for a time sufficient to blend the rubber, preferably 0.048. By thermomechanical mixing, it is meant that the between 1 to 30 minutes, more preferably 1 to 3 minutes, at rubber compound, or composition of rubber and rubber least one deblocking agent at about 0.05 to 20 parts by compounding ingredients, is mixed in a rubber mixture weight of the filler and a curing agent at 0 to 5 phr; and under high shear conditions where it autogenously heats up optionally as a result of the mixing primarily due to shear and associ ated friction within the rubber mixture in the rubber mixer. 0058 (C) curing said mixture at a temperature of 130° to Several chemical reactions may occur at various steps in the 200° C. for about 5 to 60 minutes. mixing and curing processes. 0059. The process may also comprise the additional steps 0049. The first reaction is a relatively fast reaction and is of preparing an assembly of a tire or Sulfur Vulcanizable considered herein to take place between the filler and the rubber with a tread comprised of the rubber composition SiX, group of the blocked mercaptosilane. Such reaction prepared according to this invention and Vulcanizing the may occur at a relatively low temperature Such as, for assembly at a temperature in a range of 130° to 200° C. example, at about 120°C. The second and third reactions are 0060 Suitable organic polymers and fillers are well considered herein to be the deblocking of the mercaptosilane known in the art and are described in numerous texts, of and the reaction which takes place between the sulfuric part which two examples include The Vanderbilt Rubber Hand of the organosilane (after deblocking), and the Sulfur Vul book, R. F. Ohm, ed. R.T. Vanderbilt Company, Inc., Nor canizable rubber at a higher temperature, for example, above walk Conn., 1990), and Manual for the Rubber Industry, T. about 140° C. Kempermann, S. Koch, and J. Sumner, eds. (Bayer AG, Leverkusen, Germany, 1993). Representative examples of 0050 Another sulfur source may be used, for example, in suitable polymers include solution styrene-butadiene rubber the form of elemental sulfur as Ss. A sulfur donor is (sSBR), styrene-butadiene rubber (SBR), natural rubber considered herein as a Sulfur containing compound which (NR), polybutadiene (BR), ethylene-propylene co- and ter liberates free, or elemental, Sulfur at a temperature in a range polymers (EP, EPDM), and acrylonitrile-butadiene rubber of 140° to 190° C. Examples of such sulfur donors may be, (NBR). The rubber composition is comprised of at least one but are not limited to, polysulfide Vulcanization accelerators diene-based elastomer, or rubber. Suitable conjugated dienes and organosilane polysulfides with at least two connecting are isoprene and 1,3-butadiene and Suitable vinyl aromatic sulfur atoms in its polysulfide bridge. The amount of free compounds are styrene and alpha methyl styrene. Thus, the sulfur source addition to the mixture can be controlled or rubber is a sulfur curable rubber. Such diene based elas manipulated as a matter of choice relatively independently tomer, or rubber, may be selected, for example, from at least from the addition of the aforesaid blocked mercaptosilane. one of cis-1,4-polyisoprene rubber (natural and/or synthetic, Thus, for example, the independent addition of a sulfur and preferably natural rubber), emulsion polymerization Source may be manipulated by the amount of addition prepared Styrenefbutadiene copolymer rubber, organic solu thereof and by sequence of addition relative to addition of tion polymerization prepared styrene/butadiene rubber, 3,4- other ingredients to the rubber mixture. polyisoprene rubber, isoprene/butadiene rubber, styrenefiso prene/butadiene terpolymer rubber, cis-1,4-polybutadiene, 0051. Addition of an alkyl silane to the coupling agent medium vinyl polybutadiene rubber (35 percent to 50 per system (blocked mercaptosilane plus additional free Sulfur cent vinyl), high vinyl polybutadiene rubber (50 percent to Source and/or Vulcanization accelerator) typically in a mole 75 percent vinyl), styrenefisoprene copolymers, emulsion ratio of alkylsilane to blocked mercaptosilane in a range of polymerization prepared styrene/butadiene/acrylonitrile ter /so to /2 promotes an even better control of rubber compo polymer rubber and butadiene/acrylonitrile copolymer rub sition processing and aging. ber. An emulsion polymerization derived styrene/butadiene (eSBR) might be used having a relatively conventional 0.052 A rubber composition is prepared by a process styrene content of 20 percent to 28 percent bound styrene or, which comprises the sequential steps of: for some applications, an eSBR having a medium to rela tively high bound styrene content, namely, a bound styrene 0053 (A) thermomechanically mixing, in at least one content of 30 percent to 45 percent. Emulsion polymeriza preparatory mixing step, to a temperature of 140° to 200°C., tion prepared styrene/butadiene/acrylonitrile terpolymer alternatively to 140° to 190° C., for a total mixing time of rubbers containing 2 to 40 weight percent bound acryloni 2 to 20 minutes, alternatively 4 to 15 minutes, for such trile in the terpolymer are also contemplated as diene based mixing step(s): rubbers for use in this invention. 0054 (i) 100 parts by weight of at least one sulfur 0061 The solution polymerization prepared SBR (SSBR) Vulcanizable rubber selected from conjugated diene typically has a bound styrene content in a range of 5 to 50 homopolymers and copolymers, and copolymers of at percent, preferably 9 to 36 percent. Polybutadiene elastomer least one conjugated diene and aromatic vinyl com may be conveniently characterized, for example, by having pound, at least a 90 weight percent cis-1,4-content. US 2006/0183866 A1 Aug. 17, 2006

0062 Representative examples of suitable filler materials 0068 The silica might be expected to have an average include metal oxides. Such as silica (pyrogenic and precipi ultimate particle size, for example, in the range of 0.01 to tated), titanium dioxide, aluminosilicate and alumina, sili 0.05um as determined by the electron microscope, although ceous materials including clays and talc, and carbon black. the silica particles may be even Smaller, or possibly larger, Particulate, precipitated silica is also sometimes used for in size. Various commercially available silicas may be Such purpose, particularly when the silica is used in con considered for use in this invention such as, from PPG nection with a silane. In some cases, a combination of silica Industries under the HI-SIL trademark with designations HI-SIL 210, 243, etc.; silicas available from Rhone-Poulenc, and carbon black is utilized for reinforcing fillers for various with, for example, designation of ZEOSIL 1165MP; silicas rubber products, including treads for tires. Alumina can be available from Degussa with, for example, designations used either alone or in combination with silica. The term VN2 and VN3, etc.; and silicas commercially available from "alumina' can be described herein as aluminum oxide, or Huber having, for example, a designation of HUBERSIL Al-O. The fillers may be hydrated or in anhydrous form. 8745. Use of alumina in rubber compositions can be shown, for example, in U.S. Pat. No. 5,116,886 and EP 631,982. 0069. Where it is desired for the rubber composition, which contains both a siliceous filler Such as silica, alumina 0063. The blocked mercaptosilane may be premixed, or and/or aluminosilicates and also carbon black reinforcing prereacted, with the filler particles or added to the rubber pigments, to be primarily reinforced with silica as the mix during the rubber and filler processing, or mixing stage. reinforcing pigment, it is often preferable that the weight If the silane and filler are added separately to the rubber mix ratio of such siliceous fillers to carbon black is at least 3/1 during the rubber and filler mixing, or processing stage, it is and preferably at least 10/1 and, thus, in a range of 3/1 to considered that the blocked mercaptosilane then combines in 30/1. The filler may be comprised of 15 to 95 weight percent situ with the filler. precipitated silica, alumina, and/or aluminosilicate and, cor respondingly 5 to 85 weight percent carbon black, wherein 0064. The Vulcanized rubber composition should contain the carbon black has a CTAB value in a range of 80 to 150. a sufficient amount of filler to contribute a reasonably high Alternatively, the filler can be comprised of 60 to 95 weight modulus and high resistance to tear. The combined weight of percent of said silica, alumina, and/or aluminosilicate and, the filler may be as low as about 5 to 100 phr, but is more correspondingly, 40 to 5 weight percent carbon black. The preferably from 25 phr to 85 phr. siliceous filler and carbon black may be preblended or 0065 Precipitated silicas are preferred as the filler. The blended together in the manufacture of the Vulcanized silica may be characterized by having a BET Surface area, as rubber. measured using nitrogen gas, preferably in the range of 40 0070 The rubber composition may be compounded by to 600 m/g, and more usually in a range of 50 to 300 m/g. methods known in the rubber compounding art, such as The silica typically may also be characterized by having a mixing the various sulfur-Vulcanizable constituent rubbers dibutylphthalate (DBP) absorption value in a range of 100 to with various commonly used additive materials. Examples 350, and more usually 150 to 300. Further, the silica, as well of Such commonly used additive materials include curing as the aforesaid alumina and aluminosilicate, may be aids, such as Sulfur, activators, retarders and accelerators, expected to have a CTAB surface area in a range of 100 to processing additives, such as oils, resins including tackify 220. The CTAB surface area is the external surface area as ing resins, silicas, plasticizers, fillers, pigments, fatty acid, evaluated by cetyl trimethylammonium bromide with a pH Zinc oxide, waxes, antioxidants and antioZonants, peptizing of 9. The method is described in ASTM D3849. agents, and reinforcing for materials, such as, for example, carbon black. Depending on the intended use of the sulfur 0.066 Mercury porosity surface area is the specific sur Vulcanizable and sulfur Vulcanized material (rubbers), the face area determined by mercury porosimetry. For Such additives mentioned above are selected and commonly used technique, mercury is penetrated into the pores of the sample in conventional amounts. after a thermal treatment to remove volatiles. Set up condi tions may be suitably described as using a 100 mg sample, 0071. The Vulcanization may be conducted in the pres removing volatiles during two hours at 105° C. and ambient ence of an additional Sulfur Vulcanizing agent. Examples of atmospheric pressure, ambient to 2000 bars pressure mea Suitable Sulfur Vulcanizing agents include, for example, Suring range. Such evaluation may be performed according elemental Sulfur (free Sulfur) or Sulfur donating Vulcanizing to the method described in Winslow, Shapiro in ASTM agents, for example, an amino disulfide, polymeric polysul bulletin, page 39 (1959) or according to DIN 66133. For fide, or sulfur olefin adducts which are conventionally added such an evaluation, a CARLO—ERBA Porosimeter 2000 in the final, productive, rubber composition mixing step. The might be used. The average mercury porosity specific Sur Sulfur Vulcanizing agents (which are common in the art) are face area for the silica should be in a range of 100 to 300 used, or added in the productive mixing stage, in an amount m?g. ranging from 0.4 to 3 phr, or even, in some circumstances, up to about 8 phr, with a range of from 1.5 to 2.5 phr, 0067. A suitable pore size distribution for the silica, sometimes from 2 to 2.5 phr, being preferred. alumina, and aluminosilicate according to Such mercury porosity evaluation is considered herein to be: 5 percent or 0072 Vulcanization accelerators, i.e., additional sulfur less of its pores have a diameter of less than about 10 nm: donors, may be used herein. It is appreciated that they may 60 percent to 90 percent of its pores have a diameter of 10 be, for example, of the type such as, for example, benzothia to 100 nmi; 10 percent to 30 percent of its pores have a Zole, alkyl thiuram disulfide, guanidine derivatives, and diameter of 100 to 1,000 nmi; and 5 percent to 20 percent of thiocarbamates. Representative of Such accelerators are, for its pores have a diameter of greater than about 1,000 nm. example, but are not limited to, mercapto benzothiazole, US 2006/0183866 A1 Aug. 17, 2006

tetramethyl thiuram disulfide, benzothiazole disulfide, EXAMPLES diphenylguanidine, Zinc dithiocarbamate, alkylphenoldisul fide, zinc butyl Xanthate, N-dicyclohexyl-2-benzothiazole Example 1 sulfenamide, N-cyclohexyl-2-benzothiazolesulfenamide, N-oxydiethylenebenzothiazole-2-sulfenamide, N,N-diphe Preparation of 3-(methyldiacetoxysilyl)-1-propyl nylthiourea, dithiocarbamylsulfenamide, N,N-diisopropyl thioacetate benzothioZole-2-sulfenamide, zinc-2-mercaptotoluimida 0078. A 5-liter flask was fitted with a 15-plate Oldershaw Zole, dithiobis(N-methyl piperazine), dithiobis(N beta distilling column (28 mm plate diameter), to which was hydroxy ethyl piperazine) and dithiobis(dibenzyl amine). attached a condenser and distilling head capable of provid ing a controlled and adjustable reflux ratio. Heat was Sup Other additional sulfur donors, may be, for example, thi plied to the flask using an electric heating mantle regulated uram and morpholine derivatives. Representative of such by a controller coupled to an electronic temperature regu donors are, for example, but not limited to, dimorpholine lator. The vapor temperature in the head was monitored also. disulfide, dimorpholine tetrasulfide, tetramethyl thiuram tet The system was maintained under an atmosphere of nitro rasulfide, benzothiazyl-2,N-dithiomorpholide, thioplasts, gen. Control of the vacuum was enhanced via a bleeder dipentamethylenethiuram hexasulfide, and disulfidecapro valve inserted between the cold trap and the distillation lactam. head. 0073. Accelerators are used to control the time and/or 0079 738.1 grams of 3-(methyldimethoxysilyl)-1-propyl temperature required for Vulcanization and to improve the mercaptain and 1892.2 grams of acetic anhydride were added properties of the Vulcanizate. In one embodiment, a single to the 5-liter flask. The mixture was heated with stirring until accelerator system may be used, i.e., a primary accelerator. the first drops of liquid began to collect from the head, at Conventionally and preferably, a primary accelerator(s) is which time the collection rate was adjusted to 1-2 drops per used in total amounts ranging from 0.5 to 4 phr, preferably second. Heat was Supplied to the flask at a sufficient rate so 0.8 to 1.5 phr. Combinations of a primary and a secondary as to maintain a reflux ratio of no less than 8:1, but not accelerator might be used with the secondary accelerator Sufficient to cause column flooding. The collection tempera being used in smaller amounts (of 0.05 to 3 phr) in order to ture rapidly stabilized to 54° C. The collection rate was activate and to improve the properties of the Vulcanizate. increased and adjusted to maintain a collection temperature Delayed action accelerators may be used. Vulcanization of not more than 55° C. until a total of 506 grams of a clear, colorless liquid had been collected. The distillate had an retarders might also be used. Suitable types of accelerators odor of methyl acetate and was immiscible with and unre are amines, , guanidines, thioureas, thiazoles, thi sponsive toward aqueous Sodium carbonate. Further distil urams, Sulfenamides, dithiocarbamates, and Xanthates. Pref lation began with a collection at 54° C., with a gradual erably, the primary accelerator is a Sulfenamide. If a second tendency toward higher temperatures and slower collection accelerator is used, the secondary accelerator is preferably a rates until a steady collection in the range of 115° to 120° C. guanidine, dithiocarbamate, or thiuram compound. was maintained. 650 grams of a clear, colorless liquid was collected, which had an odor of acetic acid and methyl 0074 Typical amounts of tackifier resins, if used, com acetate and demonstrated vigorous effervescence with aque prise 0.5 to 10 phr, usually 1 to 5 phr. Typical amounts of ous sodium carbonate. After cooling, an additional 361 processing aids comprise 1 to 50 phr. Such processing aids grams of acetic anhydride were added to the contents of the include, for example, aromatic, naphthenic, and/or paraflinic 5-liter flask, and the distillation was reinitiated. Collection processing oils. Typical amounts of antioxidants comprise 1 eventually stabilized at 140° C. yielding 493 grams of to 5 phr. Representative antioxidants may be, for example, distillate. The temperature in the 5-liter flask had risen to diphenyl-p-phenylenediamine and others such as those dis 180° C. whereupon the heating was stopped. Both acetic closed in the Vanderbilt Rubber Handbook (1978), pages acid and acetic anhydride could be detected in the distillate 344-46. Typical amounts of antioZonants comprise 1 to 5 by odor. Its response with aqueous Sodium carbonate was phr. Typical amounts of fatty acids, which, if used, can similar to the previous sample. A final sample of distillate include Stearic acid, comprise 0.5 to 3 phr. Typical amounts was collected under vacuum. The vacuum was regulated and of Zinc oxide comprise 2 to 5 phr. Typical amounts of waxes maintained at the level required to collect the distillate at a comprise 1 to 5 phr. Often microcrystalline waxes are used. temperature near that of the cooling water used to remove Typical amounts of peptizers comprise 0.1 to 1 phr. Typical heat from the condenser using the bleeder valve. The tem peptizers may be, for example, pentachlorothiophenol and perature in the 5-liter flask was limited to 150° C. during this dibenzamidodiphenyl disulfide. procedure. The bleeder valve gradually was opened. An additional 428 grams of distillate collected. The final distil 0075. The rubber composition of this invention can be late had an odor of acetic anhydride. At this point, the used for various purposes. For example, it can be used for temperature in the 5-liter flask was slowly increased, leading various tire compounds. Such tires can be built, shaped, to the fractional distillation of the product at <0.7 kPa. An molded, and cured by various methods which are known and initial 12-gram fraction was collected at <1 drop? second will be readily apparent to those having skill in Such art. with a reflux ratio of 10: 1. A second fraction of 950 grams 0.076 All references cited are incorporated herein as they of a clear, colorless liquid was collected at a Substantially are relevant to the present invention. faster rate with a reflux ratio of >5:1. The distillation was terminated when the temperature of the 5-liter flask reached 0077. The invention may be better understood by refer 180°C., leaving a dark brown, viscous residue of 170 grams. ence to the following examples in which the parts and The second fraction was product of 98.5 percent purity percentages are by weight unless otherwise indicated. (GC); distilled yield, 83 percent. US 2006/0183866 A1 Aug. 17, 2006

Example 2 additional 2,015 grams of acetic anhydride was added to the cooled 5-liter flask, and the distillation resumed, yielding an Preparation of 3-(trimethoxysilyl)-1-propyl additional 923 grams of distillate. The procedure was then thioacetate repeated a third time with a 701 gram addition of acetic anhydride, yielding 834 grams of distillate. The application 0080. The apparatus used was identical to that of of vacuum to the head was then begun. The vacuum was Example 1. 1,074 grams of 3-(trimethoxysilyl)-1-propyl regulated and maintained at the level required to collect the mercaptain and 561.4 grams of acetic anhydride were added distillate at a temperature near that of the cooling water used to the 5-liter flask. The system was evacuated, followed by to remove heat from the condenser via the bleeder valve. The continuous application of vacuum using the bleeder valve in temperature in the 5-liter flask was limited to 170° C. during the nearly shut position. The temperature of the 5-liter flask this procedure. The bleeder valve was opened gradually as was increased gradually to 120° C., at which time conden the collection rate began to diminish. An additional 896 sate began collecting at <30° C. The distillation was con grams of distillate collected, whereupon any remaining tinued until nothing more collected with the 5-liter flask now liquids in the column and head evaporated. GC analysis of at a temperature of 155° C., at which time the heating was the final distillate indicated that essentially nothing less stopped, yielding 184 grams of a clear, colorless liquid with volatile than acetic anhydride had distilled over. The con a distinct odor of methyl acetate. Its specific gravity of 0.898 tents of the flask cooled to a viscous, dark brown oil, which combined with a negative response to aqueous sodium was stored under nitrogen. carbonate indicated that a substantial portion of methanol was probably present. The temperature of the 5-liter flask Example 5 was now gradually raised to 195°C., yielding an additional total of 266 grams of condensate. The distillation was Preparation of continued with gradual heating of the 5-liter flask to 225°C. 3-(propionylthio)-1-propyltrimethoxysilane and with the bleeder valve open. 379 grams of a clear liquid was collected at a maximum head temperature of 104°C. 0084) 816 grams of 3-mercapto-1-propyltrimethoxysi GC analysis indicated that both the starting and product lane, 871 grams of 25 weight percent methanolic solution of silanes were major components of the distillate, with Small Sodium methoxide, and 1.724 grams of toluene were amounts of acetic acid detectable by odor. charged to a 5-liter flask under an atmosphere of nitrogen. 0081. The contents of the 5-liter flask were emptied into The stirred mixture developed a pinkish color. Methanol was and stored in a 32-oZ. (947 ml) bottle under nitrogen. The removed from the flask by distilling off a methanol-toluene 5-liter flask was charged with the distillate, which was azeotrope, during which time the contents of the flask turned redistilled with the bleeder valve wide open. A large first colorless. The appearance of a strong density current in the fraction contained mostly the starting blocked mercaptosi distillate which coincided with an increased in distillation lane. A second, clear and colorless 75 gram fraction was head temperature from 63°C. to 108°C. signaled the point collected at 70° C. This fraction was product of >90 percent at which methanol removal from the flask was complete. purity (GC); distilled yield, 6 percent. The product also With continued stirring, the contents of the flask were contained derivative containing methoxy-Si and acetoxy-Si allowed to cool and were placed in an ice-water bath. 361 grams of propionyl chloride was added to the flask dropwise groups and SiOSi crosslinks. and/or in Small portions with continued stirring in an ice Example 3 water bath until the reaction was complete. Aliquots of the stirred mixture were taken periodically and placed onto pH Preparation of 3-(trimethoxysilyl)-1-propyl paper. An alkaline reading indicated the completion of the reaction. The final mixture was a white suspension of NaCl thioacetate Derivative Containing acetoxy-Si in a toluene solution of the product. This mixture was filtered Groups and SiOSi Crosslinks and the solvent was removed from the filtrate to yield a light 0082. This product was the undistilled liquid that brown product. Gas chromatography indicated 5 percent remained in the distilling flask of Example 2 after removal 3-mercapto-1-propyltrimethoxysilane, 25 percent of 3-(me of the second, clear and colorless 75 gram fraction, which thylthio)-1-propyltrimethoxysilane, and 70 percent of was collected at 70° C. and was the product of Example 2 3-(acetylthio)-1-propyltrimethoxysilane (product). Flash of >90 percent purity (GC); distilled yield, 6 percent. distillation from one to two grams of powdered sodium methoxide yielded a colorless product. The sodium meth Example 4 oxide was added to ensure that any remaining acidity was neutralized. Further optional fractional distillation yielded a Preparation of 3-(trimethoxysilyl)-1-propyl product in excess of 98 percent purity by GC.. thioacetate Derivative Containing acetoxy-Si Groups and SiOSi Crosslinks Example 6 0083. The apparatus used was identical to that of Preparation of Example 1. 1,775 grams of 3-(trimethoxysilyl)-1-propyl 3-(propionylthio)-1-propyltrimethoxysilane mercaptain was added to the 5-liter flask. A total of 4,719 grams of acetic anhydride was set aside for reaction with the 0085 1,035 grams of 3-mercapto-1-propyltrimethoxysi mercaptosilane, of which 1,002 grams was added to the lane, 1,096 grams of a 25 weight percent methanolic solu 5-liter flask along with the mercaptosilane. The heat flow to tion of sodium methoxide, and 1,764 grams of toluene were the 5-liter flask was increased gradually until a steady charged to a 5-liter flask under an atmosphere of nitrogen. collection of distillate was established at a head temperature The stirred mixture developed a pinkish color. The flask was of 54° C. A total of 840 grams of distillate was collected, placed into a water bath at 64° C. Methanol was removed which was found to contain methyl acetate, acetic acid, and from the flask by distilling off a methanol-toluene azeotrope methanol in a 100/2/2.7 molar ratio by NMR analysis. An under a partial vacuum. The vacuum was kept Such that the US 2006/0183866 A1 Aug. 17, 2006

temperature in the distillation head was maintained at 30° to response to pH paper. Sufficient powdered sodium ethoxide 35° C. during which time 1,500 ml of distillate, consisting was stirred into the product to neutralize all of the acidity. of a toluene-methanol azeotrope, was collected. During this Flash distillation at <0.7 kPa yielded a light pink product time the contents of the flask turned colorless. An additional containing about 10 percent by gas chromatography each of 429 grams of toluene were added, and the distillation ethylbenzoate and 1-sila-2-thia-1, 1-diethoxycyclopentane, resumed. The appearance of a strong density current in the which formed because of base catalyzed decomposition distillate, which coincided with an increase in distillation during the distillation. A second flash distillation was per head temperature from 35° to 55° C., and the appearance of formed in which the first 30 percent of the product was a changing liquid Surface tension in the condenser signaled removed as a forecut. No base or acid was present. The the point at which methanol removal from the flask was second fraction was a product of light pink color in excess complete. The contents of the flask had become a viscous of 98 percent purity by G.C. fluid. With continued stirring, the contents of the flask were allowed to cool. The flask was placed in an ice-water bath, Example 8 resulting in what appeared to be a thick paste. 427 grams of propionyl chloride was added to the flask dropwise and/or in Preparation of 2-(acetylthio)-1-ethyltriethoxysilane Small portions with continued stirring in an ice-water bath until the reaction was complete. Aliquots of the stirred 0088 2.513 grams of vinyltriethoxysilane was added to a mixture were taken periodically. An alkaline reading indi 5-liter flask and brought to reflux with stirring. A 25 ml cated the completion of the reaction. The final mixture was forecut was distilled off to remove volatile impurities. The a white suspension of NaCl in a toluene solution of the heating was stopped, and a first, 335 gram, portion of a total product. This mixture was filtered, and the solvent was of two portions of 1,005 grams of thiolacetic acid was added removed from the filtrate to yield a nearly colorless product. over a period of several minutes at a rate to maintain a Gas chromatography indicated (by weight) 3 percent of smooth reflux. Heat was supplied toward the end of the 3-mercapto-1-propyltrimethoxysilane, 1 percent of 3-(me addition, as necessary, to maintain the reflux. 0.8 gram of thylthio)-1-propyltrimethoxysilane, and 96 percent of di-t-butyl peroxide was added down the condensers, result 3-(acetylthio)-1-propyltrimethoxysilane (product). Flash ing in an immediate reaction as evidenced by a reflux rate distillation from one to two grams of powdered sodium acceleration. Power to the heating mantle was cut. During methoxide yielded a colorless product. The sodium meth the reflux, the temperature rose to near 160° C. within oxide was added to ensure that any remaining acidity was several minutes, whereupon the reflux subsided and the light neutralized. Further optional fractional distillation yielded a yellow contents of the pot began to cool. product in excess of 98 percent purity by GC.. 0089. When the contents of the pot had reached 150°C., an additional 670 grams of thiolacetic acid was added in a Example 7 manner similar to the first addition. 20 ml. of forecut were collected, and 1.6 grams of di-t-butyl peroxide was again Preparation of added. A slight increase in reflux rate was observed within 3-(benzylthio)-1-propyltriethoxysilane several minutes. After 10 to 15 minutes, the pot reached a maximum temperature of 155° C. and Subsequently began to 0.086 763 grams of 3-mercapto-1-propyltriethoxysilane cool. At 150° C. the temperature was maintained by the and 1,013 grams of a 21 weight percent ethanolic solution of heating mantle for one hour. The pot was allowed to cool sodium ethoxide were charged to a 5-liter flask under an under nitrogen. Gas chromatography analysis indicated (by atmosphere of nitrogen. 850 grams of ethanol was distilled weight) 2 percent thiolacetic acid, 16 percent vinyltriethox from this mixture at a maximum temperature of 45° C. at 48 ysilane, 5 percent 1-(acetylthio)-1-ethyltriethoxysilane kPa. 1,550 grams of toluene was added to the contents of the (alpha adduct), 68 percent 2-(acetylthio)-1-ethyltriethoxysi flask under nitrogen. The remaining ethanol was removed lane (beta adduct product), and 9 percent balance (mainly from the flask by distilling off an ethanol-toluene azeotrope heavies). under a maximum absolute pressure of 48 kPa at a maximum temperature of 60° C. The vacuum was kept such that the Example 9 temperature in the distillation head was maintained at 30° to 40° C. The appearance of a strong density current in the Preparation of distillate which coincided with an increase in distillation 3-(octanoylthio)-1-propyltriethoxysilane head temperature from 35° to about 60° C. and the appear ance of a changing liquid Surface tension in the condenser 0090 Into a 12-liter, three-necked round bottom flask signaled the point at which ethanol removal from the flask equipped with mechanical stirrer, addition funnel, thermo was complete. At the end of this procedure the contents of couple, heating mantle, N inlet, and temperature controller the flask had become a clear, orange liquid. were charged 1,021 grams of 3-mercaptopropyltriethoxysi lane (SILOUESTR A-1891 silane from OSi Specialties, 0087. With continued stirring, the contents of the flask Inc., a Subsidiary of Crompton Corp. of Greenwich, Conn.), were allowed to cool to ambient temperature. 418 grams of 433 grams of triethylamine, and 3,000 ml hexane. The benzoyl chloride was added to the flask dropwise and/or in Solution was cooled in an ice bath, and 693 grams of small portions at a sufficiently slow rate to prevent the octanoyl chloride were added over a two hour period via the temperature from rising above 50° C. At the completion of addition funnel. After addition of the acid chloride was the benzoyl chloride addition, stirring was continued for an complete, the mixture was filtered two times, first through a additional day. The stirring was initially sufficiently vigor 0.1 um filter and then through a 0.01 um filter, using a ous to break up any chunks and inhomogeneities in the pressure filter, to remove the salt. The solvent was removed mixture. The resulting final mixture was a white Suspension under vacuum. The remaining yellow liquid was vacuum of NaCl in a toluene solution of the product. This mixture distilled to yield 1,349 grams of octanoylthiopropyltriethox was filtered, and the solvent was removed from the filtrate ysilane as a clear, very light yellow liquid. The yield was 87 to yield a light yellow-brown product which gave an acidic percent. US 2006/0183866 A1 Aug. 17, 2006

Example 10 to between 160° and 165° C. in approximately one minute. The masterbatch was dumped (removed from the mixer), a Preparation of 3-(acetylthio)-1-propyltriethoxysilane sheet was formed on a roll mill set at about 50° to 60° C., 0.091 This example illustrates the preparation of a thio and then allowed to cool to ambient temperature. carboxylate alkoxysilane from a salt of a thiolcarboxylic 0094. The rubber masterbatch was added to the mixer acid using as a solvent the alcohol corresponding to the with the mixer at 120 rpm and cooling water turned on full silane alkoxy group. Into a 250 ml, three-neck round bot and ram down mixed for 30 seconds. The remainder of the tomed flask equipped with magnetic stir bar, temperature ingredients was added and ram down mixed for 30 seconds. probe? controller, heating mantle, addition funnel, condenser, The mixer throat was dusted down, the mixer speed and N inlet was charged 63 grams of a 21 weight percent increased to 160 or 240 rpm so that the contents reached a sodium ethoxide in ethanol. Fifteen grams of thiolacetic acid temperature between 160° and 165° C. in approximately two was added slowly, keeping the temperature below 65° C. minutes. The rubber masterbatch was mixed for eight min The solution was allowed to cool to room temperature, and utes, and the speed of the BANBURY mixer as adjusted to 48 grams of chloropropyltriethoxysilane was added via the maintain the temperature between 160° and 165° C. The addition funnel. After addition was complete, the solution masterbatch was dumped (removed from the mixer), a sheet was heated to 70° C. for 24 hours whereupon a white solid was formed on a roll mill set at about 500 to 60°C., and then formed. Analysis of the solution by gas chromatography allowed to cool to ambient temperature. showed a 78 percent yield of acetylthiopropyltriethoxysi 0.095 The rubber masterbatch and the curatives were lane. mixed on a 6 in.x13 in. (15 cmx33 cm) two roll mill that was heated to between 50° and 60°C. The sulfur and accelerators Example 11 were added to the rubber masterbatch and thoroughly mixed on the roll mill and allowed to form a sheet. The sheet was Preparation of acetylthiomethyltriethoxysilane cooled to ambient conditions for 24 hours before it was cured. The rheological properties were measured on a Mon 0092. This example illustrates the preparation of a thio santo R-100 Oscillating Disk Rheometer and a Monsanto carboxylate alkoxysilane from a salt of a thiolcarboxylic M1400 Mooney Viscometer. The specimens for measuring acid using a nonprotic solvent. 88 grams of powdered the mechanical properties were cut from 6 mm plaques sodium ethoxide and 600 ml diglyme were charged into a cured for 35 minutes at 160° C. or from 2 mm plaques cured one-liter, three-neck round bottomed flask equipped with for 25 minutes at 160° C. magnetic stir bar, temperature probe? controller, heating mantle, addition funnel, condenser, N inlet, and ice water 0096) Silanes from Examples 2 to 4 were compounded bath. The solution was cooled to 8° C., and 105 grams of into the tire tread formulation according to the above pro thiolacetic acid was added slowly via the addition funnel, cedure. The performance of the silanes prepared in keeping the temperature below 60° C. The solution was Examples 1 to 4 was compared to the performance of no allowed to cool to 35° C., and 250 grams of chloromethyl silane coupling agent (Silane C), two silanes, one of which triethoxysilane was added via the addition funnel. After is practiced in the prior art, bis-(3-triethoxysilyl-1-propy addition was complete, the solution was heated to 70° C. 1) tetrasulfide (TESPT, Silane B), the other 3-triethoxysilyl where a brief exotherm to 120° C. was observed. The 1-propylmercaptain (TESPM, Silane Y) which is the product solution was heated at 70° C. for an additional three hours. resulting from the loss of a carboxyl blocking group from a A white solid formed which was filtered first through a 0.1 representative example of the silanes of the present inven um pressure filter and then a 0.01 um filter to give a clear, tion. The results of this procedure are tabulated below in black solution. The solvent was removed under reduced Table 2. pressure, and the remaining liquid vacuum distilled to yield TABLE 1. 163 grams of a clear and colorless liquid, a 55 percent yield. Model Low Rolling Resistance Tread Formulation Example 12 PHR Ingredient The Use of Silanes of Examples 1 to 4 in Low 75 sSBR (12% styrene, 46% vinyl, T: 42° C.) 25 BR (98% cis, T: 104°C.) Rolling Resistant Tire Tread Formulation 8O Silica (150–190 m/gm, ZEOSIL 1165 MP, Rhone-Poulenc) 32.5 Aromatic process oil (high viscosity, Sundex 8125, Sun) 0093. A model low rolling resistance passenger tire tread 2.5 Zinc oxide (KADOX 720C, Zinc Corp.) formulation as described in Table 1 up and a mix procedure 1 Stearic acid (INDUSTRENE, Crompton) were used to evaluate representative examples of the silanes 2 6PPD antiozonant (SANTOFLEX 6PPD, Flexsys) of the present invention. The silane in Example 1 was mixed 1.5 Microcrystalline wax (M-4067, Schumann) 3 N330 carbon black (Engineered Carbons) as follows in a “B” BANBURYR (Farrell Corp.) mixer with 1.4 Sulfur (#104, Sunbelt) a 103 cu. in. (1690 cc) chamber volume. The mixing of the 1.7 CBS accelerator (SANTOCURE, Flexsys) rubber masterbatch was done in two steps. The mixer was 2 DPG accelerator (PERKACIT DPG-C, Flexsys) turned on with the mixer at 120 rpm and the cooling water on full. The rubber polymers were added to the mixer and ram down mixed for 30 seconds. Half of the silica and all of 0097. The following tests were conducted with the fol the silane with approximately 35-40 grams of this portion of lowing methods (in all examples): Mooney Scorch (a) 135° silica in an ethylvinyl acetate (EVA) bag were added and ran C. (ASTM Procedure D1646); Mooney Viscosity (a 1000° down mixed for 30 seconds. The remaining silica and the oil C. (ASTM Procedure D1646); Oscillating Disc Rheometer in an EVA bag were next added and ram down mixed for 30 (ODR) (a) 149° C., 1° arc, (ASTM Procedure D2084): seconds. The mixer throat was thrice dusted down, and the Physical Properties, cured t90 (a) 149° C. (ASTM Proce mixture ram down mixed for 15 seconds each time. The dures D412 and D224) (G' and G" in dynes/cm); DIN mixer's mixing speed was increased to 160 or 240 rpm, as Abrasion, mm (DIN Procedure 53516); and Heat Build required to raise the temperature of the rubber masterbatch (ASTM Procedure D623). US 2006/0183866 A1 Aug. 17, 2006 14

TABLE 2 Performance of Representative Silanes in a Model Low Rolling Resistance Passenger Tire Tread Formulation Silane C. B Ex. 4 Ex. 3 Ex. 1 Ex. 2 y y

Amount 7.4 7.4 7.4 7.4 8.3 3.8 6.35 Mooney Viscosity at 100° C.

ML1 + 4 130 67 65 58 73 63 74 121 Mooney Scorch at 135° C. MS1+, t, minutes 9.5 6.7 4.3 6.3 2.2 6.3 6.3 2.8 MS1+, ts, 11.O 10.1 5.9 7.8 3.2 7.7 8.4 3.7 ODR (a) 149° C., 1° arc, 30 minute timer MI, dN-M 26.9 8.5 8.5 7.2 9.3 7.8 11.5 14.8 MH, dN-M 445 30.8 31.0 31.4 34.8 3O.S 27.8 33.9 t1, minutes 5.4 4.8 2.5 3.8 1.6 3.8 3.8 2.0 t0, minutes 1O.S 17.8 8.0 8.O 8.1 7.5 15.3 1S.O Physical Properties, cured t90 (a) 149° C. Hardness, Shore A 66 57 59 60 62 60 52 scorched Elongation, % 900 400 S4O 520 490 450 360 100% Mod., kg/cm 1O.S 19.0 19.0 18.3 22.5 23.2 15.5 not 200% Mod., kg/cm 15.5 56.9 49.2 46.4 59.8 66.1 45.0 cured 300% Mod., kg/cm 24.6 128.0 101.2 96.2 116.O 1294 104.8 Tensile, kg/cm 137.1 208.1 234.8 218.0 237.6 222.9 139.2 Dynamic Properties (a) 0.15% strain, 10 Hz, torsion mode (2nd Sweep) G' (a) 0° C., x 107 26.8 S.92 9.22 9.42 1.26 6.41 3.17 G' (a 60° C., x 10' 12.7 2.76 4.26 3.89 5.36 3.02 1.75 G" (a) 0° C., x 107 2.87 1.26 1.81 1.84 2.14 1.3 S.69 G" (a 60° C., x 10° 11.2 2.48 4.OO 3.85 4.94 2.71 2.13 Tan delta (a) 0° C. O.1070 O.2124 O.1968 O.1952 O.169 O.2O2 O.2O2 Tan delta (a 60° C. O.O876 O.09 O.0939 O.O988 O.O92 O.O89 O.121 Ratio O. C.60° C. 122 2.36 2.10 1.98 1.84 2.25 1.67 Heat Building-up, 100° C. ambient, 18.5% compression, 143 psi (99 kPa) load, 25 minutes Delta T, C. 66 13 22 19 18 17 Set, % ::::::::: 6.3 10.9 8.8 8.0 6.9

*** delaminated in 9 Example 13 TABLE 3-continued The Use of Silane of Example 1 in Low Rolling The Effect of DPG on the Compounding and Curing of a Model Low Resistance Tire Formulation Activated by Varying Rolling Resistance Passenger Tire Tread Formulation Levels of DPG Run A. C ODR (a) 149° C., 1° arc, 0098. The model low rolling resistance passenger tire 30 minute timer tread formulation and mixing procedure of Example 11 were MI, dN-M 9.8 9.4 8.6 used to evaluate the silane of Example 1 at three levels of M, dN-M 35.7 28.8 33.4 N,N'-diphenylguanidine (DPG). The results are tabulated tl, minutes 1.8 8.O 3.4 below in Table 3. t0, minutes 8.0 22.5 11.8 Physical properties, cured t90 (a) 149° C. TABLE 3 Hardness, Shore A 63 59 62 The Effect of DPG on the Compounding and Curing of a Model Low Elongation, % 550 62O S60 Rolling Resistance Passenger Tire Tread Formulation 100% Modulus, kg/cm 21.1 19.0 22.5 200% Modulus, kg/cm’ 55.5 42.9 55.5 Run A. B C 300% Modulus, kg/cm 106.9 80.9 106.2 Tensile, kg/cm’ 236 209.5 234.1 DIN Abrasion, mm 85 69 72 phr DPG 2.OO O.S 1.25 Dynamic properties (a) 10 Hz, Mooney viscosity (a) 100° C. 0.15 strain, torsion mode ML 1 + 4 75 G' (a) 0° C., x 107 14.8 14.1 12.6 Mooney scorch (a) 135° C. G' (a 60° C., x 10' 6.23 5.97 5.64 G" (a) 0° C., x 107 23.0 26.4 22.1 G" (a 60° C., x 10° 6.55 7.30 6.O1 My 41 Tan delta (a) 0° C. O.1551 O.1872 0.1753 MS 1+, t, minutes 2.5 15.3 6.2 Tan delta (a) 60° C. O.1053 O. 1189 O.1O3S MS 1+, ts, minutes 3.6 24.1 8.3 Ratio O. C.60° C. 1.47 1.57 1.69 US 2006/0183866 A1 Aug. 17, 2006

Example 14 MBTS, 0.5 MBT, 0.2 TMTM, Silane SILOUEST A-1289 silane (TESPT) or acetylthiopropyltriethoxysilane (Acetyl). Shoe Sole Compound Compositions The amounts of each are in phr. The term “Add Sulfur or 0099 Formulation: 60 Budene 1207 BR, 40 SMR5L NR, “Add S' means that additional sulfur was added to make the 45 ZEOSIL 1165MP Silica, 5 CALSOL 5550 Process Oil, 3 CARBOWAX 3350 PEG, 5 KADOX 720C Zinc Oxide, 1 amount of sulfur in the Acetyl equivalent to the amount of INDUSTRENE R Stearic Acid, 1 BHT Antioxidant, 1 sulfur delivered by TESPT. The results are set forth in Table SUNOLITE 240 Wax, 1.9 Rubbermakers Sulfur 104, 1.3 4 below. TABLE 4 Silane None TESPT TESPT Acetyl Acetyl Acetyl Acetyl Add Sulfur X X Amount, phr 2 4 2 2 4 4 Mooney Scorch at 135° C.

MV 51 42 40 36 33 MS1+, t, minutes S.O 4.3 4.3 6.9 7.4 MS1+, ts, minutes 5.8 5.3 5.3 8.2 8.8 Mooney Viscosity (a) 100° C.

ML1 + 4 96 78 76 74 71 ODR (a) 149° C., 1° arc, 12 minute timer MI, dN-M 19.7 14.9 14.0 12.2 11.5 10.4 10.2 MH, dN-M 59.7 57.4 54.2 S2.0 52.8 49.3 49.8 t1, minutes 3.5 2.8 2.8 4.3 3.8 4.7 4.4 t0, minutes 5.7 S.6 5.9 7.5 7.1 8.2 8.2 Physical Properties, cured t90 (a) 149 C. Hardness, Shore A 67 67 66 66 66 66 66 Elongation, % 630 570 570 S4O 440 500 460 100% Mod., kg/cm 19.7 23.9 25.3 26.7 26.7 26.7 27.4 200% Mod., kg/cm 36.6 SO.6 54.1 56.2 59.1 55.5 59.8 300% Mod., kg/cm 58.3 86.5 91.4 97.7 103.3 96.3 105.5 Tensile, kg/cm’ 1870 2O4.6 222.2 2011 1744 1898 1891 DIN Abrasion, mm 86 75 67 74 71 65 73 Akron Abrasion, mm O46 O.48 O3S O.39 O41 O45 0.44 Example 15 Low Rolling Resistance Tire Formulations 0.100 The following silanes were tested in low rolling resistance tire formulations: TESPT (A): TESPM (B): 3-acetylthio-1-propyltrimethoxysilane (C), 3-acetylthio-1- propyltriethoxysilane (D), 3-octanoylthio-1-propyltriethox ysilane (E): 3-palmitoylthio-1-propyltriethoxysilane (F); 3-ethylhexanoyl-1-propyltriethoxysilane (G): 3-propio nylthio-1-propyltrimethoxysilane (H): 3-benzoylthio-1-pro pyltriethoxysilane (I); acetylthiomethyltriethoxysilane (J), acetylthioethyltrimethoxysilane (K), acetylthioethyltri ethoxysilane (L), acetothioethylmethyldimethoxysilane (M), acetylthiooctyltrimethoxysilane (N), acetylthiooctyltri ethoxysilane (O), acetylthiocyclohexylethyltri methoxysilane (P), and acetothionorbornylethyltri methoxysilane (Q). The formulation was (amounts in phr) 75 SOLFLEX 1216 sSBR, 25 Budene 1207 BR, 80 ZEOSIL 1165MP silica, 32.5 SUNDEX 3125 process oil, 2.5 KADOX 720C zinc oxide, 1.0 INDUSTRENE R stearic acid, 2.0 SANTOFLEX 13 antiozonant, 1.5 M4067 micro wax, 3.0 N330 carbon black, 1.4 Rubbermakers sulfur 104, 1.7 CBS, 2.0 DPG, Silane as shown.

TABLE 5

Silane A. B B C C D D

Add S X X X Amount, phr 7.0 6.36 6.36 6.33 6.33 7.45 7.45 US 2006/0183866 A1 Aug. 17, 2006 16

TABLE 5-continued Mooney Viscosity at 100° C.

ML1 + 4 94 74 74 72 62 Mooney Scorch at 135° C. MS1+, t, minutes 6.2 9.9 9.0 6.9 7.5 6.3 6.3 MS1+, ts, minutes 8.9 12.6 11.5 9.3 10.2 7.6 7.8 ODR (a) 149° C., 1° arc, 30 minute timer MI, dN-M 9.6 8.1 8.1 8.7 8.5 7.9 7.7 MH, dN-M 31.8 29.5 34.5 32.O 36.7 29.9 33.9 t1, minutes 4.5 5.4 S.1 4.1 4.5 3.6 3.5 t0, minutes 17.6 10.4 14.1 11 11.5 8.0 7.5 Physical Properties, cured t90 (a) 149° C.

Hardness, Shore A 57 58 60 64 66 59 60 Elongation, % 420 S60 440 660 570 630 S4O 100% Mod., kg/cm 20.4 16.9 22.5 17.6 22.5 15.5 19.0 200% Mod., kg/cm 58.4 40.1 59.8 38.7 54.8 34.5 49.9 300% Mod. kg/cm’ 123.7 84.4 123.0 73.8 105.5 71.7 104.1 Tensile, kg/cm 210.9 210.3 2116 22S.O 250.3 223.6 236.2 DIN Abrasion mm 71 69 76 114 97 131 90 Heat Build-up (a) 100° C., 17.5% compression, 99 kPa static, 25 minute run Delta T, C. 13.3 18.9 13.3 32.2 18.3 21.1 13.3 Permanent set, % 6.2 1O.S 6.3 25.3 12.3 14.5 9.8 Dynamic Properties (a) 0.15% strain, 10 Hz, torsion mode G' (a) 0° C., dyn/cm x 10' 6.73 12.8 12.4 20.1 16.6 12.8 10.4 G' (a 60° C., dyn/cm x 107 3.00 S.13 5.15 8.73 2.67 S.10 1.93 G" (a) 0° C., dyn/cm2 x 107 1.46 2.44 2.43 3.39 7.06 2.47 4.OS G" (a 60° C., dyn/cm x 10 2.93 5.23 4.47 8.35 5.33 5.79 3.21 Tan delta (a) 0° C. O.216 O.191 O.196 0.168 0.161 O.192 O.185 Tan delta (a) 60° C. O.098 0.102 O.O87 0.096 O.O75 O.114 O.O79 Ratio O. C.60° C. 2.22 1.88 2.26 1.75 2.15 1.68 2.34

Silane E E F F G H H

Add S X X X Amount, phr 9.69 12.67 12.67 9.62 6.7 6.7 Mooney Viscosity at 100° C.

ML1 + 4 55 50 52 66 Mooney Scorch at 135° C. MS1+, t, minutes 10.4 9.6 13.0 11.9 16.8 8.3 7.7 MS1+, ts, 11.7 11.7 14.6 13.9 19.0 9.9 9.6 ODR (a) 149° C., 1° arc, 30 minute timer M, dN-M 6.7 6.8 5.7 5.7 5.5 8.2 7.9 MH, dN-M 27.8 32.3 26.8 30.7 31.6 30.1 34.6 t1, minutes S.6 5.5 7.0 6.8 9.1 4.5 4.4 t0, minutes 11.3 9.8 12.3 11.O 14.1 9.5 9.0 Physical Properties, cured t90 (a) 149° C.

Hardness, Shore A 53 55 51 S4 56 58 60 Elongation, % 600 490 740 610 600 610 S4O 100% Mod., kg/cm 14.1 17.6 12.7 15.5 15.5 16.2 20.4 200% Mod. kg/cm’ 34.5 49.2 27.4 36.6 35.9 38.0 52.7 300% Mod., kg/cm 77.3 105.5 55.5 71.O 69.6 80.2 108.3 Tensile, kg/cm’ 227.8 213.7 205.3 186.3 175.8 234.1 244.7 DIN Abrasion mm 99 92 157 127 94 Heat Build-up (a) 100° C., 17.5% compression, 99 kPa static, 25 minute run Delta T, C. 12.2 8.9 1O.S 18.9 12.21 Permanent set, % S.O 4.6 7.0 11.O 7.7 Dynamic Properties (a) 0.15% strain, 10 Hz, torsion mode G' (a) 0° C., dyn/cm2 x 107 4.80 4.62 6.40 5.93 9.29 10.1 9.54 G' (a 60° C., dyn/cm x 107 2.44 O.82 2.42 1.13 1.88 4.18 1.76 G" (a) 0° C., dyn/cm x 107 O.98 2.00 1.27 2.17 3.64 2.07 3.72 G" (a 60° C., dyn/cm2 x 10 2.14 1.27 2.34 1.23 3.08 4.62 2.72 Tan delta (a) 0° C. O.2OS O.177 O.199 O.191 O.202 0.2OS O.184 Tan delta (a) 60° C. O.O88 0.064 O.097 0.057 0.085 O-110 O.O73 Ratio O. C.60° C. 2.33 2.77 2.05 3.35 2.39 1.86 2.52 US 2006/0183866 A1 Aug. 17, 2006

TABLE 5-continued

Silane I J K K L L M M

Add S X X X Amount, phr 9.1 6.7 S.96 S.96 7.08 7.08 S.S4 S.S4 Mooney Viscosity at 100° C.

ML1 + 4 55 69 73 63 71 Mooney Scorch at 135° C. MS1+, t, minutes 11.5 2.5 4.6 4.3 4.5 4.6 4.7 4.9 MS1+, ts, 13.5 3.5 S.6 S.6 5.3 S.6 5.8 6.1 ODR (a) 149° C., 1° arc, 30 minute timer MI, dN-M 6.2 8.8 9.5 9.0 6.8 7.7 9.4 9.3 M, dN-M 3S.O 32.5 29.8 34.1 27.5 31.3 33.9 38.1 t1, minutes 6.3 1.9 2.8 2.8 2.8 2.8 3.0 2.9 t0, minutes 11.3 17.0 16.8 15.3 11.3 9.5 13.5 11.8 Physical Properties, cured t90 (a) 149° C.

Hardness, Shore A 62 61 61 65 56 58 66 65 Elongation, % S60 440 500 470 S8O S60 530 530 100% Mod., kg/cm 19.0 19.0 19.0 20.4 14.8 17.6 21.2 22.5 200% Mod., kg/cm 47.8 51.3 43.6 51.3 33.7 42.9 47.1 55.5 300% Mod., kg/cm 107.5 109.0 84.4 105.5 69.6 91.4 87.9 105.5 Tensile, kg/cm 210.9 1982 1849 2O8.1 1990 234.8 196.9 225.7

Silane I J K K L L M

DIN Abrasion mm 133 88 113 103 133 96 101 Heat Build-up (a) 100° C., 17.5% compression, 99 kPa static, 25 minute run Delta T, C. 12.8 15.6 21.7 16.1 28.9 16.7 2S.O Permanent set, % 7.9 10.8 13.7 8.7 23.2 11.2 17.3 Dynamic Properties (a) 0.15% strain, 10 Hz, torsion mode G' (a) 0° C., dyn/cm x 10' 17.9 10.8 18.2 16.1 10.1 8.94 27.7 G' (a 60° C., dyn/cm x 107 2.99 2.16 6.60 2.70 4.30 1.73 9.54 G" (a) 0° C., dyn/cm2 x 107 6.38 3.92 3.27 5.86 2.12 3.65 4.33 G" (a 60° C., dyn/cm x 10 6.83 4.87 941 S.92 5.32 2.92 14.O Tan delta (a) 0° C. O.167 0.2O1 O.180 0.167 O.210 O.193 O.156 Tan delta (a) 60° C. O.107 O.124 O.143 0.101. O.124 O.O8O O.147 Ratio O. C.60° C. 1.56 1.67 1.26 1.65 1.69 2.41 1.06

Silane M N N O O P Q

DIN Abrasion mm 96 1OO 94 113 97 141 132 Heat Build-up (a) 100° C., 17.5% compression, 99 kPa static, 25 minute run Delta T, C. 16.7 21.1 15.6 14.4 17.2 1S.O Permanent set, % 9.2 16.8 12.6 11.O 12.7 10.8 Dynamic Properties (a) 0.15% strain, 10 Hz, torsion mode G' (a) 0° C., dyn/cm2 x 107 22.2 14.9 12.4 10.2 8.10 27.6 23.8 G' (a 60° C., dyn/cm x 107 3.39 5.72 2.33 4.25 1.55 3.72 3.59 G" (a) 0° C., dyn/cm x 107 7.79 2.93 4.85 2.06 2.80 10.8 9.04 G" (a 60° C., dyn/cm2 x 10 9.17 5.75 3.62 4.06 2.44 12.4 9.61 Tan delta (a) 0° C. O.153 O.197 0.187 0.2O2 O.192 O.13S O.151 Tan delta (a) 60° C. O.118 0.101 O.O75 0.096 O.087 O.115 O. 106 Ratio O. C.60° C. 1.30 1.9S 2.49 2.10 2.21 1.18 1.42

1-19. (canceled) each R is chosen independently from hydrogen, straight, 20. A filled rubber produced by a process comprising the cyclic, or branched alkyl that may or may not contain steps of mixing a rubber, an inorganic filler, and a blocked unsaturation, alkenyl groups, aryl groups, and aralkyl mercaptosilane of the formula groups, with each R containing from 1 to 18 carbon atoms; each G is independently a monovalent or polyvalent wherein group derived by Substitution of alkyl, alkenyl, aryl, or aralkyl wherein G can contain from 1 to 18 carbon Y is a polyvalent species (Q)A(=E), each wherein the atoms, with the proviso that if Y is —C(=O)—, G is atom A attached to the unsaturated heteroatom E is not such that the blocked mercaptosilane would contain attached to the sulfur, which in turn is linked via a an unsaturated carbonyl, and if G is univalent, G can be group G to the silicon atom; a hydrogen atom; US 2006/0183866 A1 Aug. 17, 2006

X is independently a group selected from the group 29. The filled rubber of claim 20 wherein the blocked consisting of C1, Br, RO RC(=O)C , mercaptosilane is selected from the group consisting of RC=NO RNO , RN —R, and 2-triethoxysilyl-1-ethyl thioacetate; 2-trimethoxysilyl-1- —(OSiR),(OSiR) wherein each R is as above and at ethyl thioacetate: 2-(methyldimethoxysilyl)-1-ethyl least one X is not —R; thioacetate; 3-trimethoxysilyl-1-propylthioacetate; tri Q is oxygen, Sulfur, or ( NR—); ethoxysilylmethyl thioacetate; trimethoxysilylmethyl thioacetate; triisopropoxysilylmethyl thioacetate; A is carbon, Sulfur, phosphorus, or Sulfonyl: methyldiethoxysilylmethyl thioacetate; meth yldimethoxysilylmethyl thioacetate; methyldiisopro E is oxygen, sulfur, or NR; poxysilylmethyl thioacetate; dimethylethoxysilylm p is 0 to 5; r is 1 to 3; Z is 0 to 2: j is 0 to 1, but it may ethyl thioacetate; dimethylmethoxysilylmethyl be 0 only if p is 1; t is 0 to 5; s is 1 to 3; k is 1 to 2, thioacetate; dimethylisopropoxysilylmethyl thioac with the provisos that (A) if A is carbon, sulfur, or etate, 2-triisopropoxysilyl-1-ethyl thioacetate: 2-(me sulfonyl, then k is 1; and (B) if A is phosphorus, then thyldiethoxysilyl)-1-ethyl thioacetate: 2-(methyldiiso k is 2: propoxysilyl)-1-ethyl thioacetate; 2-(dimethylethoxysilyl-1-ethyl thioacetate: 2-(dimeth to produce a rubber mixture: ylmethoxysilyl)-1-ethyl thioacetate: 2-(dimethyliso mixing into the rubber mixture (i) a deblocking agent to propoxysilyl)-1-ethyl thioacetate; 3-triethoxysilyl-1- deblock the blocked mercaptosilane, and (ii) a curing propyl thioacetate; 3-triisopropoxysilyl-1-propyl agent; and thioacetate; 3-methyldiethoxysilyl-1-propyl thioac etate; 3-methyldimethoxysilyl-1-propyl thioacetate; allowing the rubber mixture to cure. 3-methyldiisopropoxysilyl-1-propyl thioacetate, 1-(2- 21. The filled rubber of claim 20 wherein each R of the triethoxysilyl-1-ethyl)-4-thioacetylcyclohexane: 1-(2- blocked mercaptosilane is selected from the group consist triethoxysilyl-1-ethyl)-3-thioacetylcyclohexane: 2-tri ing of methyl, ethyl, propyl, isobutyl, phenyl, tolyl, phen ethoxysilyl-5-thioacetylnorbomene: 2-triethoxysilyl-4- ethyl, norbornyl, norbornenyl, ethylnorbornyl, ethylnor thioacetylnorbomene: 2-(2-triethoxysilyl-1-ethyl)-5- bornenyl, ethylcyclohexyl, ethylcyclohexenyl, and thioacetylnorbomene: 2-(2-triethoxysilyl-1-ethyl)-4- cyclohexylcyclohexyl. thioacetylnorbornene; 1-(1-oxo-2-thia-5- 22. The filled rubber of claim 20 wherein the blocked triethoxysilylpenyl)benzoic acid: 6-triethoxysilyl-1- mercaptosilane has the formula: hexylthioacetate: 1-triethoxysilyl-5-hexylthioacetate; 8-triethoxysilyl-1-octyl thioacetate: 1-triethoxysilyl-7- octyl thioacetate; 6-triethoxysilyl-1-hexyl thioacetate; 23. (canceled) 1-triethoxysilyl-5-octyl thioacetate; 8-trimethoxysilyl 24. The filled rubber of claim 20 wherein the blocked 1-octyl thioacetate: 1-trimethoxysilyl-7-octyl thioac mercaptosilane is partially hydrolyzed. etate; 10-triethoxysilyl-1-decyl thioacetate: 1-triethox ysilyl-9-decyl thioacetate: 1-triethoxysilyl-2-butyl 25. The filled rubber of claim 20 wherein Y of the blocked thioacetate: 1-triethoxysilyl-3-butyl thioacetate: 1-tri mercaptosilane is selected from the group consisting of ethoxysilyl-3-methyl-2-butyl thioacetate: 1-triethox ysilyl-3-methyl-3-butyl thioacetate: 3-trimethoxysilyl 1-propyl thiooctanoate; 3-triethoxysilyl-1-propyl-1- propyl thiopalmitate; 3-triethoxysilyl-1-propyl thiooctanoate: 3-triethoxysilyl-1-propyl thiobenzoate: 3-triethoxysilyl-1-propylthio-2-ethylhexanoate: 3-me thyldiacetoxysilyl-1-propylthioacetate; 3-triacetoxysi lyl-1-propyl thioacetate; 2-methyldiacetoxysilyl-1- ethyl thioacetate: 2-triacetoxysilyl-1-ethyl thioacetate; 1-methyldiacetoxysilyl-1-ethyl thioacetate: 1-triac etoxysilyl-1-ethyl thioacetate; tris-(3-triethoxysilyl-1- propyl)trithiophosphate; bis-(3-triethoxysilyl-1-propy l)methyldithiophosphonate: bis-(3-triethoxysilyl-1- 26. The filled rubber of claim 20 wherein each G of the propyl)ethyldithiophosphonate; 3-triethoxysilyl-1- blocked mercaptosilane is independently a monovalent or propyldimethylthiophosphinate; 3-triethoxysilyl-1- polyvalent group derived by Substitution of alkyl, alkenyl, propyldiethylthiophosphinate; tris-(3-triethoxysilyl-1- aryl, or aralkyl wherein the sum of all carbon atoms within propyl)tetrathiophosphate; bis-(3-triethoxysilyl-1- G groups is three to eighteen carbon atoms. propyl)methyltrithiophosphonate; bis-(3 27. The filled rubber of claim 20 wherein each G of the -triethoxysilyl-1-propyl)ethyltrithiophosphonate; 3-tri blocked mercaptosilane is independently a monovalent or ethoxysilyl-1-propyldimethyldithiophosphinate; 3-tri polyvalent group derived by Substitution of alkyl, alkenyl, ethoxysilyl-1-propyldiethyldithiophosphinate; tris-(3- aryl, or aralkyl wherein the sum of all carbon atoms within methyldimethoxysilyl-1-propyl)trithiophosphate; bis G groups is six to fourteen carbon atoms. (3-methyldimethoxysilyl-1- 28. The filled rubber of claim 20 wherein X of the blocked propyl)methyldithiophosphonate; bis-(3- mercaptosilane is independently selected from the group methyldimethoxysilyl-1- consisting of methoxy, ethoxy, isobutoxy, propoxy, isopro propyl)ethyldithiophosphonate; poxy, acetoxy, and oximato. 3-methyldimethoxysilyl-1-propyldimethylthiophosphi US 2006/0183866 A1 Aug. 17, 2006 19

nate; 3-methyldimethoxysilyl-1-propyldiethylthio to produce a rubber mixture; phosphinate; 3-triethoxysilyl-1-propylmethylthiosul phate: 3-triethoxysilyl-1- mixing into the rubber mixture (i) a deblocking agent to propylmethanethiosulphonate: 3-triethoxysilyl-1-3- deblock the blocked mercaptosilane, and (ii) a curing triethoxysilyl-1-propylbenzenethiosulphonate; agent; and 3-triethoxysilyl-1-propyltoluenethiosulphonate; 3-tri allowing the rubber mixture to cure. ethoxysilyl-1-propylnaphthalenethiosulphonate; 3-tri 31. A filled rubber produced by a process comprising the ethoxysilyl-1-propylxylenethiosulphonate; triethoxysi steps of mixing a rubber, an inorganic filler, and a blocked lylmethylmethylthiosulphate: mercaptosilane triethoxysilylmethylmethanethiosulphonate; triethox ysilylmethylethanethiosulphonate; triethoxysilylmeth (ROC(=O))-(G), I-Y SI-G-(SiX). (1) ylbenzenethiosulphonate; triethoxysilylmethyltolu wherein enethiosulphonate; triethoxysilylmethylnaphthalenethiosulphonate; and triethoxysilylmethylxylenethiosulphonate. R is hydrogen or an alkyl having from one to four carbon 30. A filled rubber produced by a process comprising the atoms; steps of each G is a substituted phenyl or an alkyl derivative mixing a rubber, an inorganic filler, and a blocked mer having from 2 to 12 carbonatoms, with the proviso that captosilane of the formula G is not such that the mercaptosilane would contain an W.-unsaturated carbonyl that can undergo polymer (ROC(=O))-(G)=Y SI-G(SIXs), (1) ization reactions; wherein X is independently a group selected from the group Y is a polyvalent species (Q)A(=E) selected from the consisting of C1, Br, RO RC(=O)C) , group consisting of —C(=NR)——SC(=NR)—: RC=NO RNO , RN —R, and —(OSiR),(OSiR) wherein each R and G is as above and at least one X is not —R; and p is 2 to 5; r is 1 to 3: j is 1; t is 0 to 5: s is 1 to 3; and k is 1: to produce a rubber mixture; mixing into the rubber mixture (i) a deblocking agent to deblock the blocked mercaptosilane, and (ii) a curing agent; and allowing the rubber mixture to cure. —( NR)P(=S)—; wherein the atom A, attached to 32. The filled rubber of claim 31 wherein the blocked the unsaturated heteroatom E, is attached to the sulfur mercaptosilane is partially hydrolyzed. which in turn is linked via a group G to the silicon 33. The filled rubber of claim 31 wherein X of the blocked atom; mercaptosilane is selected from the group consisting of methoxy, ethoxy, isobutoxy, propoxy, isopropoxy, acetoxy, each R is selected from the group consisting of hydrogen, and oximato. phenyl, isopropyl, cyclohexyl, and isobutyl, 34. The filled rubber of claim 31 wherein X of the blocked each G is a substituted phenyl or substituted straight chain mercaptosilane is RO - or RC(=O)C)—. alkyl having from 2 to 12 carbon atoms; 35. The filled rubber of claim 31 wherein R of the blocked mercaptosilane is hydrogen. X is independently selected from the group consisting of 36. (canceled) RO and RC(=O)C)—, wherein each R is as above: 37. The filled rubber of claim 31 wherein G, which is p is 0 to 2: r is 1 to 3; Z is 0 to 2: j is 0 to 1, but it may directly bonded to Y, is alkyl of two to twelve carbon atoms. be 0 only if p is 1; t is 0 to 5; s is 1 to 3; k is 1 to 2: 38. (canceled) with the proviso carbon, sulfur or sulfonyl, then k is 1: and (II) if A is phosphorus, then k is 2: